CN109641366A - Subparticle composition - Google Patents
Subparticle composition Download PDFInfo
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- CN109641366A CN109641366A CN201780038033.7A CN201780038033A CN109641366A CN 109641366 A CN109641366 A CN 109641366A CN 201780038033 A CN201780038033 A CN 201780038033A CN 109641366 A CN109641366 A CN 109641366A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/005—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process employing compositions comprising microparticles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/16—Inorganic impregnating agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/16—Inorganic impregnating agents
- B27K3/22—Compounds of zinc or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/34—Organic impregnating agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/34—Organic impregnating agents
- B27K3/36—Aliphatic compounds
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
- A01N59/20—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K2240/00—Purpose of the treatment
- B27K2240/20—Removing fungi, molds or insects
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Forests & Forestry (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Zoology (AREA)
- Dentistry (AREA)
- Plant Pathology (AREA)
- Pest Control & Pesticides (AREA)
- Environmental Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Toxicology (AREA)
- Dispersion Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Disclose a kind of method for preparing the composition comprising metal salt subparticle.The method includes to provide to wrap metalliferous alkaline aqueous solution, one or more ligands that can form soluble complexes with metal under alkaline condition and optional one or more dispersing agents;And mix solution to reduce the pH of solution with carbon dioxide source, so as to metal salt subparticle precipitating.Also disclose the composition prepared by the method.A kind of method for handling the matrix as timber is also disclosed, it includes the matrixes for applying the composition and handling by the method.
Description
Technical field
The present invention relates to a kind of methods for preparing the composition comprising metal salt subparticle, and are related to passing through the method
The composition of preparation.The invention further relates to a kind of methods for handling matrix, and it includes application compositions, and are related to through the side
The matrix of method processing.
Background technique
The method of composition of the preparation comprising subparticle may include right presence or absence of water or solvent
Or mixtures thereof compound is ground.In wood preservation industry, metallic compound is wet milled as submicron-scale in recent years;
These compounds generally comprise copper carbonate or Kocide SD.
The composition being thusly-formed can be used to handle the matrix as timber.Processing method can be according to application composition
Whether the property and infiltration matrix surface of matrix need composition and change.Many known methods include that biocide is very molten
Liquid, biocide suspension or fine suspension, encapsulated biocide and biocide lotion or microemulsion are as example.
Such as ligno-cellulosic materials would generally be handled after cutting down and grinding trees with biocide, to prolong
Its long service life.Plant living is usually just handled in growth, to make for good health and promote the good production of crop
Rate.Leather (animal hide) is handled after processing fresh meat.All these organic matrixs all can be by degradation biological body (example
Such as bacterium, fungi and insect) attack.In the presence of the other matrixes for the attack that may be subjected to this organism, such as spraying
The surface of object and concrete.This attack can reduce the service life of these matrixes, make appearance degradation, and can be due to failure
And generate alternative cost or potential hazard.Degradation may reduce crop yield in plant etc..
Pass through various physics using the product of different characteristics to slow down to be developed by these pest infections or infection
The method that process handles these matrixes with various chemicals.
Lignocellulosic matrix includes complex structure comprising the wood cell interconnected by pit, the pit packet
Film is included, valve system is in addition acted also as when Qi Dangshu is living.When attempting to handle the inside of the matrix, this cell and cell connect
Connecing can hinder preservative to flow into matrix.It is especially true when matrix is dry, this is because pit membrane can aspirate, that is,
Say that they can collapse into the either side of pit and effectively close it.But due to needing space preservative, with
Preservative is dried matrix before being handled critically important.
Certain modern preservatives of timber include ammoniacal copper quaternary (Ammoniacal Copper Quaternary) and copper azoles
(Copper Azole) etc..They require addition ammonia or amine to dissolve copper component, and they must be protected in use
It stays in the composition.Ammonia is a kind of toxic gas, can also be caused damages to staff other than increasing cost.Make
Ammonia is substituted with amine, but they can be such that cost deteriorates.
A kind of important component of ammoniacal copper quaternary composition is copper carbonate, also referred to as basic copper carbonate.Conventional production method packet
Acid copper sulfate solution is included to react with sodium carbonate.All compositions of copper carbonate containing ammonia are all true solutions, can be promoted into matrix
Dipping, but be therefore corrosive by there is dissolved cation copper substance, and be easy from processed matrix
It leaches.
Many conventional solubles as chromated copper arenate (Copper Chrome Arsenate) and ammoniacal copper quaternary are killed livestock
One problem of agent is corrosiveness.In the Res fungibiles for attempting not will receive disadvantage influence in industry.
Preservative or biocidal composition can also be used in matrix living, including be used to handle plant.It must not wrap carefully
Include phytotoxic component.Such as it must be without too high amount for being applied to the insecticide of plant living or fungicide
Organic solvent, such as dimethylbenzene, this is because this may result in Plant death.In addition, fungicide must be about as neutrality
Otherwise pH may cause damages to plant.Most of cupric plant protection product is all based on insoluble compound, and main cause is
Soluble copper compound is toxic to plant, and is easy to be washed into environment.Routine for plant it is insoluble it is copper-based kill it is true
The example of microbial inoculum includes the Bordeaux mixture comprising Kocide SD, and the mixing of the Burgundy comprising basic copper carbonate
Object.
This compound may further be used to handle abiotic matrix, such as leather, concrete etc..
Similarly, metallic compound can be used as pigment and catalyst in many industrial circles.
Performance can be significantly increased when metallic compound is made of low particle size.This includes biocide, pigment and urges
Agent.A trend present in the present age is using smaller and smaller particle size, including nano particle.Due to higher biology
Availability and/or higher pigmentation and/or higher catalytic value, these metallic compounds preferably have the particle ruler of very little
Very little and big surface area, to enhance its biological nature, visual characteristic or catalysis characteristics.
The present age biocidal composition include may be inflammable, toxic, environmentally harmful component.Selected biocidal
Any component except agent all can increase cost for composition.
Colloidal state water preservative was in the public eye close to 100 years.For example, GB387819 introduction uses colloidal state trisulfides two
Ascu saves timber.
In order to handle timber etc., particle size should be less than 1 micron, otherwise may block up into the passage aisle of matrix
Plug, it is poor so as to cause the infiltration and distribution of preservative.
One of the performance of the sub-micron biocide prepared by wet grinding may be will affect when for wood preservation
Problem is wood matrix with the neutral pH between 4 and 5.By wet grinding prepare sub-micron biocide usually have 7 with
PH between 10, therefore since the buffer function of matrix may become unstable when being used to and handling acid higher timber,
Especially when using vacuum/pressurized repetitive cycling technology in treatment process.Antiseptic composition frequently makes in many circulations
With, therefore the particle kinetics in the composition may change, this may will affect particle size.If particle size increases
If adding, because there is the possibility penetrated into and be deteriorated in the blocking in channel.
Similarly, for containing sub-micron pigment (especially inorganic pigment, such as green copper carbonate, white zinc carbonate, shallow
Green nickelous carbonate, cupric oxide, green copper borate) composition there are markets.All these compounds are used equally for ceramics
And it is used as catalyst.It may include this pigment in timber preservative to enhance the color of processing timber.It is also expensive for producing them
's.
Transition metal oxide is used as catalyst.Example includes that cupric oxide nano particle is used in the catalysis oxidation of methanol
With nickel oxide nano particle.It include zinc oxide and copper oxide for converting the catalyst of carbon monoxide and hydrogen.
Persistently there is demand in the method for the composition to preparation comprising metal salt subparticle.
The purpose of the present invention is meet this needs, and/or at least useful choosing of public's offer to a certain extent
It selects.
Other purposes of the invention may become apparent from by being described below for providing by way of example.
Any discussion of the file, movement, material, device, the product that include in this specification etc. only merely for be the present invention
The purpose of background is provided.Should not be construed as recognizing any or all these content formed prior art basis a part or
It is well known general knowledge in field related to the present invention, exists before priority date just as it the same.
Summary of the invention
In one aspect, the present invention provides a kind of method for preparing the composition comprising metal salt subparticle, the side
Method includes:
It provides and wraps metalliferous alkaline aqueous solution, one or more can form soluble complexes with metal under alkaline condition
Ligand and optional one or more dispersing agents;
Solution is mixed with carbon dioxide source to reduce the pH of solution, so as to metal salt subparticle precipitating, to provide
Water-based composition comprising metal salt subparticle.
On the other hand, the present invention provides a kind of method for preparing the composition comprising metal salt subparticle, described
Method includes:
It provides and wraps metalliferous alkaline aqueous solution, one or more can form soluble complexes with metal under alkaline condition
Ligand and one or more dispersing agents;
Solution is mixed with carbon dioxide source to reduce the pH of solution, so as to metal salt subparticle precipitating, to provide
Water-based composition comprising metal salt subparticle.
Following embodiment and can preferably relate separately to or with wherein two or more any any combination be related to
Upper aspect and other aspects herein.
In various embodiments, the water-based composition comprising subparticle is colloidal dispersion;Or include subparticle
Water-based composition be flocculated composition, and the method further include by the composition go flocculation to provide colloidal state
Dispersion.
In various embodiments, the water-based composition comprising subparticle is colloidal dispersion.
In various embodiments, the water-based composition comprising subparticle is flocculated composition;And the method into
One step includes to go flocculation to provide colloidal dispersion flocculated composition.
In various embodiments, go flocculation comprising diluting the composition flocculated composition.
In other embodiments, go flocculation comprising being ultrasonically treated to the composition flocculated composition.
In various embodiments, solution is mixed to the pH that can reduce solution with carbon dioxide source, so as to metal carbonate Asia
Microparticle precipitating.
In various embodiments, solution is mixed to the pH that can reduce solution with carbon dioxide source, so as to metal borate Asia
Microparticle precipitating.In some embodiments, metal carbonate subparticle and metal borate subparticle precipitating and/or
The subparticle of metal carbonate and metal borate precipitating.
In various embodiments, soluble metal complex compound is decomposed when reducing the pH of alkaline solution.
In various embodiments, the carbon dioxide reaction that soluble metal complex compound can be provided with carbon dioxide source.
In various embodiments, one or more ligands of soluble metal complex compound are discharged from soluble metal complex compound, and
And/or the salt of one or more ligands of person's soluble metal complex compound is generated by the decomposition of soluble metal complex compound.
In various embodiments, one or more ligands for being discharged or its generated salt can reduce or prevent Asia
The aggregation and/or sedimentation of microparticle.
In certain embodiments, one or more ligands for being discharged or its generated salt are selected from ammonium carbonate, amine
Carbonate and glycol.
In various embodiments, the solution further includes the source of one or more acid.In various embodiments, institute
State the source that solution further includes one or more weak acid.
In various embodiments, the method includes and mixes solution, carbon dioxide source and one or more weak acid (inciting somebody to action
Solution mixed with carbon dioxide source before, in the process and/or later) to reduce the pH of solution, so that metal salt subparticle is heavy
It forms sediment.
In various embodiments, the weak acid is the pKa at least about 6,6.5,7,7.5,8,8.5,9,9.5 or 10
Weak acid.In various embodiments, pKa be about 6 to 15,6 to 14,6 to 13,6 to 12,6 to 11,6 to 10,6 to 9.5 or 6 to
9。
In various embodiments, the weak acid be in the water of pH7 can with metal be formed essentially insoluble property salt it is weak
Acid.In various embodiments, the weak acid is the salt that can also form essentially insoluble property with metal in the water that pH is about 8 to 9
Weak acid.
In various embodiments, the weak acid is boric acid or phenol.
In various embodiments, the weak acid is boric acid.
In various embodiments, the weak acid is boric acid, and the metal salt precipitated includes metal borate.
In various embodiments, the method includes by source of boric acid (such as boric acid or borate) and to include metal carbonate
The composition of subparticle mixes, to provide the composition for including metal borate subparticle.
In various embodiments, weak acid source is boric acid or borate.
In various embodiments, weak acid source is borax.
In various embodiments, the metal salt precipitated includes the salt of weak acid.
In various embodiments, the water-based composition includes metal carbonate subparticle, and the method is into one
Step will be comprising that will include that the water-based composition of metal carbonate subparticle is handled with alkali (such as alkali metal hydroxide), to provide
Water-based composition comprising metal hydroxides subparticle.In various embodiments, the alkali is alkali or alkaline earth metal
Hydroxide.
In various embodiments, the water-based composition includes the subparticle of metal carbonate or metal hydroxides,
The method is further included by the water-based composition comprising metal carbonate subparticle or comprising metal hydroxides Asia
The water-based composition of microparticle heats, to provide the water-based composition for including metal oxide subparticle.
In various embodiments, the source of carbon dioxide is carbon dioxide gas, wraps carbonated solution, is potential
Carbon dioxide source or the wherein arbitrarily combination of two or more.
In various embodiments, the source of carbon dioxide is carbon dioxide gas or the carbonated solution of packet, institute
The metal salt of precipitating is metal carbonate.
In various embodiments, the source of carbon dioxide is carbon dioxide gas or the carbonated solution of packet.
In certain embodiments, the source of carbon dioxide is carbon dioxide gas.
In various embodiments, the source of carbon dioxide be carbon dioxide gas, and in (for example) high-pressure reactor
Carbon dioxide gas is mixed with alkaline aqueous solution under pressure (pressure for being greater than atmospheric pressure).
In certain embodiments, the source of carbon dioxide is to wrap carbonated solution.
In various embodiments, carbonated solution is wrapped to be saturated by carbon dioxide.
In other embodiments, the source of carbon dioxide is potential carbon dioxide source.
In various embodiments, potential carbon dioxide source is organic carbonate (such as ethylene carbonate or carbonic acid diformazan
Ester).
In various embodiments, the source of carbon dioxide is organic carbonate, and method includes by solution and mixing
Organic carbonate heating, to increase the rate that organic carbonate is decomposed into carbon dioxide.
In various embodiments, the method is further contained under agitation and mixes solution with carbon dioxide source.It is described
Agitation is preferably high shear.
In various embodiments, metal salt has the solubility less than 0.1g/L at 20 DEG C in water, such as at 20 DEG C
Under less than 0.01,0.009,0.008,0.007,0.006,0.005,0.004,0.003 or 0.002g/L.For example, copper carbonate exists
There is at 20 DEG C 1.46x10 in water-5The solubility of g/L, and Kocide SD then has 1.722x 10 at 20 DEG C-7G/L's
Solubility.
In various embodiments, the pH of solution be reduced to pH be about 4.5 to about 10, for example, about 4.5 to 9.5,5 to 10,5 to
9.5,5 to 9,5.5 to 10,5.5 to 9.5,5.5 to 9.
In various embodiments, it is about 4.5 to about 9 that the pH of solution, which is reduced to pH,.
In various embodiments, it is about 6 to about 10 that the pH of solution, which is reduced to pH, for example, from about 6 to 9.5,6 to 9,6.5 to
10,6.5.To 9.5,6.5 to 9,7 to 10,7 to 9.5,7 to 9,7.5 to 10,7.5 to 9.5,7.5 to 9,8 to 10,8 to 9.5 or
8 to 9.
In certain embodiments, it is about 7.5 to about 9.5 that the pH of solution, which is reduced to pH,.
In various embodiments, it is about 8 to about 9 that the pH of solution, which is reduced to pH,.
In various embodiments, providing alkaline aqueous solution includes: providing packet metalliferous alkaline precursor aqueous solution and one
Kind or a variety of ligands that can form soluble complexes with metal under alkaline condition;And
Optionally mix one or more dispersing agents.
In various embodiments, providing alkaline aqueous solution includes:
The metalliferous alkaline precursor aqueous solution of packet is provided and one or more can be formed under alkaline condition with metal can
The ligand of molten complex compound;And
Mix one or more dispersing agents.
In various embodiments, alkaline solution is provided or alkaline precursor solution is included in comprising alkali (such as sodium hydroxide, hydrogen
Potassium oxide, ammonia or amine) aqueous alkalescence medium in by source metal and it is one or more under alkaline condition can with metal formed can
The ligand reaction of molten complex compound.
In various embodiments, the alkali be alkali metal hydroxide (such as sodium hydroxide or potassium hydroxide), ammonia or
Amine.
In various embodiments, source metal is metallic compound or metal element.In various embodiments, source metal is gold
Belong to salt or metal element.In the exemplary embodiment, source metal is metal salt.
In various embodiments, the pH of alkaline solution and/or alkaline precursor solution be at least 9,9.5,10,10.5,11,
11.5,12,12.5,13,13.5 or 14, useful range can be selected from any two in these values, for example, from 9 to 14,9 to
13.5,9 to 13,9 to 12.5,9 to 12,9 to 11.5,9 to 11,9 to 10.5,9 to 10,9.5 to 14,9.5 to 13.5,9.5 to
13,9.5 to 12.5,9.5 to 12,9.5 to 11.5,9.5 to 11,9.5 to 10.5,9.5 to 10,10 to 14,10 to 13.5,10 to
13,10 to 12.5,10 to 12,10 to 11.5,10 to 11 or 10 to 10.5.
In various embodiments, one or more of ligands are selected from the group being made up of: ammonia, amine and glycol,
Such as dihydric alcohol, trihydroxylic alcohol and polyalcohol.
In the exemplary embodiment, one or more of ligands are selected from the group being made up of: glycerol, second two
Alcohol and ammonia.
In various embodiments, the soluble complexes are-two alcohol complex of metal, metal-ammonia complex or metal-
Amine complex.
In various embodiments, described to form complex compound with cognition and metal, it is insoluble under alkaline condition, in neutral pH
Under it is unstable.In various embodiments, soluble metal complex compound is decomposed when reducing the pH of alkaline solution.
In various embodiments, the metal is first, second or third transition series metal.
In various embodiments, the metal is nickel, copper or zinc.In the exemplary embodiment, the metal be copper or
Zinc.
In the exemplary embodiment, the metal is copper (II) or zinc (II).In certain embodiments, the metal is
Copper (II).
In various embodiments, alkaline aqueous solution and/or alkaline precursor aqueous solution and/or water-based composition include it is a kind of or
A variety of organic solvents.
In various embodiments, one or more organic solvents are miscible with water.In other embodiments, institute
It is not miscible with water for stating one or more organic solvents.
In various embodiments, one or more solvents can be at above-critical state.In various embodiments, one or more
Solvent can be the supercritical solvent mixed with cosolvent.
In various embodiments, the alkaline aqueous solution comprising subparticle and/or alkaline precursor aqueous solution and/or aqueous group
It closes object and further includes one or more surfactants.
In various embodiments, the method is further included by one or more surfactants and comprising subparticle
Alkaline aqueous solution and/or alkaline precursor aqueous solution and/or water-based composition mixing.
In various embodiments, the method is further included by one or more other dispersing agents and comprising sub-micro
Alkaline aqueous solution and/or the water-based composition mixing of grain.One or more other dispersing agents can in alkaline solution
It is identical or different through existing one or more dispersing agents.
In various embodiments, the dispersing agent are as follows: anionic dispersing agents, such as polycarboxylate (such as polyacrylic acid
Salt), naphthalenesulfonate formaldehyde condensation compound, ligninsulfonate, condensate of melamine sulfonate and formaldehyde, alkyl-aryl-group ether phosphate,
Or alkyl ether phosphate;Cation dispersing agent;Non-ionic dispersing agent, such as polyethers (including mixed polyethers) or polyvinyl pyrrole
Alkanone;Amphoteric ion dispersing agent, such as amphoteric ion polymer;Or the wherein arbitrarily combination of two or more.
In certain exemplary embodiments, the dispersing agent is polyacrylate, polyethers, naphthalene sulphonate formaldehyde condensation
Object or the wherein arbitrarily combination of two or more.
In certain exemplary embodiments, the dispersing agent be polyacrylate or polyethers, or combinations thereof.
In various embodiments, the surfactant is: anionic surfactant, such as dodecyl benzene sulfonic acid
Salt, lauryl sulfate or lauryl sulfate;Cationic surfactant, such as benzalkonium chloride or cetyl front three
Base ammonium bromide;Nonionic surfactant, such as nonylphenol polyoxyethylene ether or octyl phenol polyoxyethylene ether;Amphoteric ion surface
Activating agent;Or the wherein arbitrarily combination of two or more.
In various embodiments, the surfactant is neopelex, lauryl sodium sulfate, lauryl
Sodium sulphate, benzalkonium chloride, cetyl trimethylammonium bromide, nonylphenol polyoxyethylene ether, octyl phenol polyoxyethylene ether or its
In two or more any combination.
In various embodiments, the method, which is further included, adjusts the alkalinity comprising subparticle by mixed acid or alkali
The pH of solution and/or alkaline precursor solution and/or water-based composition.In various embodiments, the method further includes logical
Cross the alkaline aqueous solution and/or alkaline precursor aqueous solution and/or water-based composition for adding that the adjusting of sour or alkali includes subparticle
pH。
In various embodiments, pH is adjusted by mixed weak acids or weak base.
In various embodiments, pH is adjusted by addition weak acid or weak base.
In various embodiments, pH is adjusted by mixing boric acid and/or borate (such as borax).In various realities
It applies in example, pH is buffered by mixing boric acid and/or borate (such as borax).
In certain embodiments, it is about 6 to 10 that the pH of the water-based composition comprising subparticle, which is adjusted to pH, for example, about
6 to 9.5,6 to 9,6.5 to 10,6.5.To 9.5,6.5 to 9,7 to 10,7 to 9.5,7 to 9,7.5 to 10,7.5 to 9.5,7.5 to
9,8 to 10,8 to 9.5 or 8 to 9.In certain embodiments, the pH of the water-based composition comprising subparticle is adjusted to pH and is
About 7.5 to 9.5.In certain exemplary embodiments, it is about 8 that the pH of the water-based composition comprising subparticle, which is adjusted to pH,
To 9.
In various embodiments, the water-based composition comprising subparticle is at the standard conditions (i.e. in 25 DEG C and atmosphere
Under pressure) within 1 day, 2 days, 3 days, 4 days, 5 days, 6 days or 7 days period to cohesion and/or settlement stability colloidal dispersion
Body.
In various embodiments, colloidal dispersion is at the standard conditions at least one moon, 2 months, 3 months, 4 months, 5
It is steady to cohesion and/or sedimentation in a month, 6 months, 7 months, 8 months, 9 months, 10 months, 11 months or 12 months period
It is fixed.
In various embodiments, it is deposited in and is carried out at a temperature of 0 and 80 DEG C.
In certain embodiments, precipitating carries out at ambient temperature.
In various embodiments, the method is further included the water-based composition concentration comprising subparticle.
In various embodiments, the water-based composition comprising subparticle passes through centrifugal concentrating.
In various embodiments, the water-based composition comprising subparticle is dehydrated to form slurry and/or dry and forms powder
End.
In various embodiments, the composition comprising subparticle is biocidal composition.
In certain embodiments, biocidal composition is dispersion, such as colloidal dispersion, it includes mantoquita, zinc salt or
The subparticle of a combination thereof.
In the exemplary embodiment, biocidal composition is the dispersion comprising basic copper carbonate subparticle.
In the exemplary embodiment, dispersion is water-borne dispersions.
In various embodiments, biocidal composition, which further includes, one or more helps biocide.
In various embodiments, the composition comprising subparticle further includes one or more biocides.
In various embodiments, biocide is fungicide, insecticide, mildewcide, bactericide or algicide.
In various embodiments, the method is further included by one or more biocides and comprising subparticle
Composition mixing.
In various embodiments, biocide is solution, lotion, microencapsulated form, or is subparticle.
In various embodiments, biocide is organic biocide.
In various embodiments, the method includes that mixing includes organic biocide and one or more organic solvents
Solution (mixes the composition comprising subparticle and the solution comprising organic biocide and one or more organic solvents
It closes).
In various embodiments, organic biocide is: fungicide, including Bravo, iodo propinyl butylamino
One of formic acid esters etc. is a variety of;Insecticide, including bifenthrin, decis, Permethrin, imidacloprid etc.;Bactericide
Deng;Or mixtures thereof.This list is interpreted as illustrative rather than restrictive.
In various embodiments, the composition comprising subparticle further includes the sub-micro of one or more biocides
Particle.
In certain embodiments, the composition includes basic copper carbonate subparticle and Tebuconazole or propiconazole
Subparticle or microemulsion or combinations thereof.
In certain embodiments, the composition includes basic copper carbonate subparticle and Bravo subparticle.
In certain embodiments, the composition include basic copper carbonate subparticle and quaternary ammonium compound, tertiary amine or
Tertiary amino oxides.
In various embodiments, the composition includes borate and basic copper carbonate subparticle.
In certain embodiments, the composition includes basic copper carbonate subparticle and insecticide (such as bifenthrin)
Subparticle.This composition can be used to handle plant, or include in the resin for being used to prepare force fit plate or laminated veneer lumber
In.
In various embodiments, the organic solvent comprising organic biocide is miscible in water.
In various embodiments, organic solvent be alcohol (such as C1-6 alcohol), ketone, lactams, glycol ethers or wherein any
The combination of two or more.
In various embodiments, C1-6 alcohol be methanol, ethyl alcohol, or combinations thereof.
In various embodiments, the composition comprising subparticle is comprising the metal salt subparticle through pigment coloring
Color compositions.
In various embodiments, the subparticle can reflect or absorb the light in visible wavelength region, thus described group
It closes object and obtains color.
In various embodiments, the composition comprising subparticle is carbon monoxide-olefin polymeric, and it includes with catalysis characteristics
Metal salt subparticle.
In certain embodiments, the method includes:
It provides and wraps metalliferous alkaline aqueous solution, one or more can form soluble complexes with metal under alkaline condition
Ligand, optional one or more dispersing agents and optional one or more weak acid source, wherein the metal is copper
(II) or zinc (II), one or more of ligands are selected from ammonia, amine and glycol, so that solvable metal complex is metal-ammino
Close object ,-two alcohol complex of metal-amine complex or metal;
Solution is mixed with carbon dioxide source to reduce the pH of solution, so as to metal salt subparticle precipitating, to provide
Water-based composition comprising metal salt subparticle,
Wherein the water-based composition is colloidal dispersion, or is gone flocculation to provide colloidal dispersion.
In certain embodiments, the method includes:
It provides and wraps metalliferous alkaline aqueous solution, one or more can form soluble complexes with metal under alkaline condition
Ligand and one or more dispersing agents, wherein the metal is copper (II) or zinc (II), the choosing of one or more of ligands
From ammonia, amine and glycol, so that solvable metal complex is metal-ammonia complex, metal-amine complex or metal-glycol complexing
Object;
The source of solution, carbon dioxide source and optional one or more weak acid is mixed, to reduce the pH of solution,
So as to metal salt subparticle precipitating, so that the water-based composition comprising metal salt subparticle is provided,
Wherein the water-based composition is colloidal dispersion, or is gone flocculation to provide colloidal dispersion.
In certain embodiments, the method includes:
It provides and wraps metalliferous alkaline aqueous solution, one or more can form soluble complexes with metal under alkaline condition
Ligand and optional one or more dispersing agents, wherein the metal be copper (II) or zinc (II), it is one or more of
Ligand is selected from ammonia, amine and glycol, so that solvable metal complex is metal-ammonia complex, metal-amine complex or metal-two
Alcohol complex;
Solution is mixed with carbon dioxide source to reduce the pH of solution, so as to metal carbonate subparticle precipitating and/
Or metal borate subparticle precipitating, so that providing includes metal carbonate subparticle and/or metal borate sub-micro
The water-based composition of particle;
Wherein the water-based composition comprising subparticle is colloidal dispersion, or is gone flocculation to provide colloidal dispersion
Body.
In certain embodiments, the method includes:
It provides and wraps metalliferous alkaline aqueous solution, one or more can form soluble complexes with metal under alkaline condition
Ligand and optional one or more dispersing agents, wherein the metal be copper (II) or zinc (II), it is one or more of
Ligand is selected from ammonia, amine and glycol, so that solvable metal complex is metal-ammonia complex, metal-amine complex or metal-two
Alcohol complex;
Solution is mixed with carbon dioxide source to reduce the pH of solution, so as to metal carbonate subparticle precipitating, thus
Water-based composition comprising metal carbonate subparticle is provided;And
It include metal hydrogen-oxygen to provide optionally by the water-based composition alkali process comprising metal carbonate subparticle
The water-based composition of compound subparticle;And/or
Optionally by the water-based composition comprising metal carbonate subparticle or include metal hydroxides sub-micro
The water-based composition heating of grain, to provide the water-based composition for including metal oxide subparticle,
Wherein the water-based composition comprising subparticle (includes the composition of sub-micron metal carbonate particle, includes
The composition of sub-micron metal hydroxide particles and/or composition comprising sub-micron metal carbonate particle) it is colloidal state point
Granular media, or gone flocculation to provide colloidal dispersion.
In certain embodiments, the method includes:
It provides and wraps metalliferous alkaline aqueous solution, one or more can form soluble complexes with metal under alkaline condition
Ligand and one or more dispersing agents, wherein the metal is copper (II) or zinc (II), the choosing of one or more of ligands
From ammonia, amine and glycol, so that solvable metal complex is metal-ammonia complex, metal-amine complex or metal-glycol complexing
Object;
Solution is mixed with carbon dioxide source to reduce the pH of solution, so as to metal carbonate subparticle precipitating, thus
Water-based composition comprising metal carbonate subparticle is provided;And
It include metal hydrogen-oxygen to provide optionally by the water-based composition alkali process comprising metal carbonate subparticle
The water-based composition of compound subparticle;And/or
Optionally by the water-based composition comprising metal carbonate subparticle or include metal hydroxides sub-micro
The water-based composition heating of grain, to provide the water-based composition for including metal oxide subparticle,
Wherein the water-based composition comprising subparticle (includes the composition of sub-micron metal carbonate particle, includes
The composition of sub-micron metal hydroxide particles and/or composition comprising sub-micron metal carbonate particle) it is colloidal state point
Granular media, or gone flocculation to provide colloidal dispersion.
In various embodiments, the method be in order to generate the metalliferous carbonate of packet, hydroxide, oxide or
The composition of the subparticle of borate.
In various embodiments, it includes metal carbonate, metal hydroxides or metal oxygen that the method, which is to generate,
The composition of the subparticle of compound.
In various embodiments, when being tested using AWPAE12 Corrosion standards method, the composition and standard ACQ phase
At least low by 20% mpy than that can generate, for example, at least low 30%, at least low 40%, at least low 50%, at least low 60%, at least
Low 70%, at least low 80% or at least low 90%.In various embodiments, mpy at least low 60%.In another embodiment,
The composition will not show corrosion.
On the other hand, the present invention provides through prepared according to the methods of the invention comprising metal salt subparticle
Composition.
On the other hand, the present invention provides a kind of method for handling matrix, and the method includes to apply basis to matrix
The composition comprising metal salt subparticle of method preparation of the invention.
In various embodiments, the composition passes through dipping, spray, spraying, brushing, mixing or positive pressure dipping, vacuum
Pressure impregnation or its modification are applied to matrix.
In various embodiments, by the composition be applied to matrix can assign matrix Biocidal properties, coloring properties or
Catalysis characteristics.
In various embodiments, face can be assigned at least one target area of matrix by the composition being applied to matrix
Color or hydrophobicity.
In certain embodiments, the processing is to protect matrix from harmful organism organism on matrix or matrix
Harmful organism organism is perhaps removed or is prevented harmful organism organism in matrix by interior growth from matrix or in matrix
Upper or base tumor growth, or alleviate harmful organism organism on matrix or base tumor growth.
In various embodiments, matrix to be processed is organic matrix.
In various embodiments, described matrix is lignocellulosic matrix.
In other embodiments, described matrix is inorganic matrix, such as concrete or stone.
In various embodiments, the composition is applied to matrix at ambient temperature.
It in various embodiments, is stable under substrate temperature of the composition when applying.
On the other hand, the present invention provides the matrix according to the method processing for handling matrix according to the present invention.
Both as used herein, term "and/or" refers to "and" or "or", or refer to.
Term "comprising" as used in this description refer to " at least partly by ... form.When including term " packet
Containing " the specification in explain each narrative tense, before with the term that feature or the feature except those features
May exist.The relational language as " including (comprise) " and " including (comprise) " should be explained in the same manner.
The present invention can also widely advocate to include in present specification with two or more in component, element or feature
Any combination of kind or the independent component for referring to or pointing out or refer to jointly or point out of all combinations, elements and features, at this
Specific integer is referred in text and the integer is in field of the present invention in the case where have equivalent, it is this known
Equivalent be believed to comprise herein, it is the same just as individually being illustrated.
It is also all reasonable within the scope of this including referring to be intended to when referring to numberical range (such as 1 to 10) disclosed herein
Numerical value (such as 1,1.1,2,3,3.9,4,5,6,6.5,7,8,9 and 10), and further include referring to reasonable value within the scope of this
Any range (such as 2 to 8,1.5 to 5.5 and 3.1 to 4.7), therefore, clear disclosed all ranges is all herein
Subrange is specifically disclosed herein.These examples being only especially desired to, between cited minimum and peak
The all possible combinations of numerical value should all be counted as clearly stating in a similar way in this application.
Although the present invention is carrying out the definition of wide scope above, it will be understood by those skilled in the art that the present invention is not
It is confined to this, the invention also includes each embodiments, are described below and provide the example.
Detailed description of the invention
The description present invention with reference to the drawings, in the accompanying drawings:
Fig. 1 is the photo of the sample of the copper carbonate subparticle dispersion prepared in example 1, shows that the dispersion is
It is optically transparent.
Fig. 2 is the photo of the sample of the copper carbonate subparticle dispersion prepared in example 1, and display is when LED light source
Light beam passes through the muddiness observed when sample.
Fig. 3 is the chart for showing the particle size distribution of the dispersion formed in example 1.
Fig. 4 is the scanning electron micrograph (SEM) of the dispersion granule formed in example 7.
Specific embodiment
Inventors hereof have unexpectedly found that subparticle biocide, pigment and catalyst can be simple and have
Effect ground from optionally including the metal complex alkaline aqueous solution precipitating of one or more dispersing agents by preparing.
Device and the device fabrication of simple cheap can be used not to lead without the use of expensive milling apparatus for subparticle
High-energy cost or cooling cost are caused, the solvent or surfactant of large volume are not needed yet.Subparticle is convenient to connecing
It is manufactured closely or in lesser manufacturing cell positioned at final field of employment.
The Biocidal composition prepared by wet grinding, especially subparticle composition, it is necessary to be generated concentrating on
Large volume is prepared in the manufacturing cell to minimize cost, and composition of the invention then can field of employment simply and economically
It generates.
Therefore, in one aspect, the method for the composition the present invention relates to preparation comprising metal salt subparticle.Substantially and
Speech, the method comprise the steps of:
It provides and wraps metalliferous alkaline aqueous solution, one or more can form soluble complexes with metal under alkaline condition
Ligand and optional one or more dispersing agents;And
Solution is mixed with carbon dioxide source to reduce the pH of solution, so as to metal salt subparticle precipitating, to provide
Water-based composition comprising metal salt subparticle.
On the other hand, the method for the composition the present invention relates to preparation comprising metal salt subparticle, the method
Include:
It provides and wraps metalliferous alkaline aqueous solution, one or more can form soluble complexes with metal under alkaline condition
Ligand and one or more dispersing agents;And
Solution is mixed with carbon dioxide source to reduce the pH of solution, so as to metal salt subparticle precipitating, to provide
Water-based composition comprising metal salt subparticle.
As used herein, term " subparticle " refers to that particle does not all have in any side more than or equal to 1 micron
Size.As used herein, term " particle size " refers to the size of the maximum dimension of particle.
Technology well known by persons skilled in the art can be used to measure for particle size, such as laser diffraction, photon correlation spectroscopy
Method, sedimentation field flow fractionation, disk centrifuge filtration method or inductor section.In various embodiments, " subparticle " has at least 0.005
Micron and the particle size less than 1 micron, for example, at least 0.01 micron and less than 1 micron.Water comprising metal salt subparticle
Property composition may include with the particle greater than 1 micron of particle.But in certain embodiments, existing this particle
Amount is preferably lower, is, for example, less than 30%, 20%, the 10% of particle or is greater than 1 micron less than the 5% of particle.
Metal can be the transition metal selected from first, second or third transition series.Metal may be at any suitable
Oxidation state.In the exemplary embodiment, metal is zinc or copper, such as Zn (II) or Cu (II).
The method can be used to provide comprising various different metal salt (such as the carbonate of metal, hydroxide, oxidation
Object and borate) subparticle composition.
In certain embodiments, metal salt be copper carbonate, Kocide SD, copper oxide, copper borate, zinc carbonate, zinc hydroxide,
Zinc oxide or zinc borate.In certain embodiments, metal salt is copper carbonate, Kocide SD, copper oxide, zinc carbonate, hydroxide
Zinc or zinc oxide.In certain embodiments, metal salt is copper carbonate, Kocide SD, copper oxide or zinc carbonate.In certain demonstrations
In the embodiment of property, metal salt is basic copper carbonate.In other exemplary embodiments, metal salt is zinc carbonate.
It can be provided in the form of streaming flow the composition comprising subparticle prepared by the method, such as colloidal state
Dispersion, slurry or powder.Also granule can be converted by the composition.In certain embodiments, the composition is to have
The aqueous fluids form of active component provides, and the component is non-volatile at the temperature at which application.
In order to provide slurry or powder, the water-based composition comprising subparticle can be concentrated, to reduce in composition
The amount of liquid.The composition can be concentrated by various modes, including centrifugation, filtering, dialysis, infiltration, electrophoresis etc..Picture chlorine,
Soluble ion as nitrate anion, sulfate radical, sodium, potassium etc. can be removed by dialysis or by centrifugation and washing.Concentration can relate to
And it is dehydrated to form slurry, and/or be related to dry to form powder.
The composition can provide in the form of dispersion.Unless otherwise noted, otherwise as used herein term " divides
Granular media " refers to a kind of homogeneous (uniform) fluid or powder, and wherein metal salt subparticle is evenly dispersed in entire powder or fluid.
In certain embodiments, the water-based composition comprising subparticle is colloidal dispersion.The dispersion includes packet
Include the aqueous continuous phase and discontinuous phase of metal salt subparticle.Colloid or colloidal dispersion are generally comprised with about 1 to about
The particle of 1000 nanometers of particle size.Transparent colloid usually has particle of the particle size less than 700 nanometers.The presence of colloid
It can be determined by observation Tyndall effect.In Tyndall effect, the light of light beam is when light beam passes through colloid by colloid
Particle scattering, otherwise it is sightless (such as Fig. 1 and seen in fig. 2) for naked eye.
The water-based composition may include flocculated metal salt subparticle.In such an embodiment, the method can be into
One step includes the step of the composition is gone flocculation, to provide colloidal dispersion.Go flocculation (or peptization) that can pass through
Any suitable way carries out, such as by carrying out ultrasonic treatment to composition or dilute composition, for example, with liquid phase its
The dilution of its component (such as other water or dispersing agent).Go flocculation that can also carry out by mixing one or more deflocculants.
The composition can be concentration form or use formulation form, such as be suitble to directly be applied to matrix (example
Such as timber) composition.In various embodiments, concentrate includes by weight of the composition about 0.1 to 30% water,
Such as by weight of the composition 0.1 to 25,0.1 to 20,0.1 to 15,0.1 to 10,0.1 to 5,0.5 to 30,0.5 to
25,0.5 to 20,0.5 to 15,0.5 to 10,0.5 to 5,1 to 30,1 to 25,1 to 20,1 to 15,1 to 10 or 1 to 5% water,
And useful range can be selected from any two in these values.In various embodiments, i.e., with formulation comprising pressing described group
Close object poidometer about 80 to 99.5% water, such as by weight of the composition 85 to 99.5,90 to 99.5 or 95 to
99.5% water, and useful range can be selected from any two in these values.
The amount of metal salt can change according to target application in the composition.In various embodiments, the composition
Comprising based on the dry weight of the composition about 50 to 95% metal salt, such as based on the dry weight of the composition 50 to 90,50
To 85,50 to 80,50 to 75,55 to 95,55 to 90,55 to 85,55 to 80,55 to 75,60 to 95,60 to 90,60 to 85,60
To 80,60 to 75,65 to 95,65 to 90,65 to 85,65 to 80,65 to 75,70 to 95,70 to 90,70 to 85,70 to 80 or
70 to 75% metal salt, and useful range can be selected from any two in these values.
Water-based composition may include one or more organic solvents and/or one or more surfactants.Organic solvent
It can be polar, nonpolar, miscible with water or not miscible with water.
The composition can be the biocidal composition comprising biocidal metal salt subparticle.Biocidal of the invention
Composition can contain polarized and/or nonpolar solvent etc., or contain surfactant or dispersing agent, so as to when needed for most
Whole Biocidal composition assigns specific characteristic.It will be understood by a person skilled in the art that various combinations of the invention can be applied to
Object.
By way of example, impregnation of timber can pass through the various vacuum or pressure of the fluid containing biocide of the invention
Power is realized.Alternatively, the fluid for containing biocide of the invention can be sprayed to plant.There is hydrophobic property in desired matrix
Or in the case where different colours, composition may include that or can be used containing certain for making those of water-proofing treatment to matrix
The composition of dyestuff or pigment, to paint to matrix.
Alternatively, the composition can be color compositions or carbon monoxide-olefin polymeric.Color compositions include through face
Expect the subparticle of the metal salt of coloring.Carbon monoxide-olefin polymeric includes the metal salt subparticle with catalysis characteristics.
Suitable pigment includes but is not limited to green copper carbonate, white zinc carbonate, light green color nickelous carbonate, black oxidation
Copper and green copper borate.All these salt are used equally for ceramics, also act as catalyst.It may include this in timber preservative
Kind pigment, to enhance the color of handled timber.
Transition metal oxide is used as catalyst.Example includes nanoparticle copper oxide and nickel oxide, is used for methanol
Catalysis oxidation.It with the catalyst of hydrogen reacted include zinc oxide and copper oxide for carbon monoxide.The oxidation of nanoparticle metal
Object can be prepared by heating metal carbonate as described herein.
It can be stabilization for agglomerating and/or settling in the water-based composition comprising subparticle of colloidal dispersion form
's.Dispersion at the standard conditions-i.e. under environment temperature (25 DEG C) and atmospheric pressure 1 day, 2 days, 3 days, 4 days, 5 days, 6
It or 7 days or 1 month, 2 months, 3 months, 4 months, 5 months, 6 months, 7 months, 8 months, 9 months, 10 months, 11
It can be in the period of the moon or 12 months stable.
One or more dispersing agents may be present in the composition, to stablize subparticle without (for example) settling
And/or aggregation.The amount of dispersing agent, the type of dispersing agent and addition opportunity can be used to adjust the particle size of the composition and steady
It is qualitative.
The water-based composition may include one or more dispersing agents.Any proper amount of point may be present in the composition
Powder.In various embodiments, one or more dispersing agents are can effectively provide stable water-based composition colloidal dispersion
Amount exists.
In various embodiments, the composition comprising subparticle includes about 5 to 50% based on the dry weight of the composition
One or more dispersing agents, such as based on the dry weight of the composition about 5 to 45,5 to 40,5 to 35,5 to 30,5 to 25,5
To one kind of 20,5 to 15,10 to 50,10 to 45,10 to 40,10 to 35,10 to 30,10 to 25,10 to 20 or 10 to 15%
Or a variety of dispersing agents, and useful range can be selected from any two in these values.In various embodiments, the composition
Include based on the dry weight of the composition about 5 to 50% one or more dispersing agents.
The dispersing agent can be known to the skilled in the art a series of one of dispersing agents.The dispersing agent can
To be organic dispersing agent, anionic dispersing agents, cation dispersing agent, non-ionic dispersing agent or amphoteric ion dispersion can be
Agent.In some embodiments, the dispersing agent is polymer, such as anionic polymer, cationic polymer, non-ionic polymeric
Object or amphoteric ion polymer.For example, the dispersing agent may is that anionic dispersing agents, such as polycarboxylate, naphthalene sulfonate
Formaldehyde condensation products, ligninsulfonate, condensate of melamine sulfonate and formaldehyde, alkyl-aryl-group ether phosphate or alkyl ether phosphates
Salt;Cation dispersing agent;Or non-ionic dispersing agent, such as polyethers (including mixed polyethers) or polyvinylpyrrolidone;Or
Person's amphoteric ion dispersing agent, such as amphoteric ion polymer;Or the wherein arbitrarily combination of two or more.Cation dispersion
The example of agent include but is not limited to dialkyl amido replace acrylates, such as dimethylamino replace acrylates,
Polyethyleneimine etc..Anionic dispersing agents may include sulfate radical, sulfonate radical, phosphonate radical, phosphate radical or carboxyl.
The composition also may include one or more surfactants.One or more surfactants can be into one
Step stablizes the subparticle in the composition.Surfactant can be carried out according to the compatibility of one or more dispersing agents
Selection.
Any suitable surfactant can be used.Surfactant can be organic surface active agent, can be yin
Ionic surface active agent, cationic surfactant, nonionic surfactant or zwitterionic surfactant.Example packet
It includes (but being not limited to): anionic surfactant, such as dodecyl benzene sulfonate, lauryl sulfate or dodecyl sulphur
Hydrochlorate;Cationic surfactant, such as benzalkonium chloride or cetyl trimethylammonium bromide;Nonionic surfactant, example
Such as polyvinylpyrrolidone, nonylphenol polyoxyethylene ether or octyl phenol polyoxyethylene ether;Zwitterionic surfactant etc..
Other than metal salt subparticle (it can be biocidal), the composition also may include one or more
Biocide.It may include biocide and/or help biocide to realize specific purpose, such as to expand the composition controllable
The organism range of system.
Composition comprising metal salt subparticle can be with one or more solution, lotion, microencapsulation or subparticle
The biocide of form mixes.The biocide of solution form may include biocide and one or more organic solvents.
The example of biocide includes but is not limited to fungicide, insecticide, mildewcide, bactericide, algicide
Deng.Biocide can be organic biocide or inorganic biocidal agent, such as borate.
Organic biocide is well-known to those skilled in the art, and including (for example) pyrrole,
Quaternary ammonium compound, fluorinated compound and combinations thereof.Organic biocide may is that fungicide, including Bravo, iodopropynyl
One of base butyl carbamate, quaternary ammonium compound, triazole compounds etc. are a variety of;Insecticide, including bifenthrin, bromine
Cyano chrysanthemate, Permethrin, imidacloprid etc.;Bactericide etc.;Or mixtures thereof.
Biocide can be water-soluble or water-insoluble.The example of water soluble biocide includes quaternary ammonium compounds
Object, such as zephiran, dimethyl didecyl ammonium chloride, dimethyl didecyl ammonium carbonate/dimethyl didecyl
Base ammonium hydrogen carbonate etc..The example of water-insoluble biocide includes but is not limited to: pyrrole, for example, Cyproconazole, propiconazole,
Tebuconazole, (TCMTB), 2- (Extraction kinetics sulfydryl), benzothiazole, Bravo and Euparen;Isothiazolone, such as
Kathon930, KathonWT, methylisothiazolinone, benzisothiazole-3-ketone and 2- octyl -3- isothiazolone;Pyrrole
Worm quinoline;Butylamino formic acid iodine propine base ester (IPBC);Pyrethroid, such as bifenthrin, cypermethrin and chlorine chrysanthemum
Ester;Poison barnyard grass with poison;4- cumyl phenol;Fipronil;Carbendazim;Cyfloxylate;And 4- α-cumyl phenol.
In various embodiments, biocide is fungicide.In various embodiments, fungicide is selected to the wooden rotten load
The group of the active fungicide of daughter bacteria.In various embodiments, fungicide includes raw selected from the pure and mild ergosterol of azoles
One or more fungicides of the group of object synthetic inhibitor, to prevent the growth of white rot, brown rot and soft rotten fungi, it is not
In the timber of processing the main reason for decay of wood.The example of azoles alcohol includes Climbazole, clotrimazole, imazalil, dislikes imidazoles, miaow
Fresh amine, fluorine bacterium azoles, oxygen ring azoles, bromuconazole, cyproconazole, diclobutrazol, Difenoconazole, olefin conversion, Da Keli, epoxiconazole, second ring
Azoles, benzoxazole, Fluquinconazole, Flusilazole, Flutriafol, furconazole, furconazole_cis, hexaconazole, amide azoles, kind bacterium azoles, the special seat that goes out, nitrile bacterium
Azoles, penconazole, propiconazole, prothioconazoles, quinconazole, simeconazoles, Tebuconazole, tetraconazole, triazolone, Triadimenol,
Triticonazole, uniconazole P and Dan Kesu.The example of ergosterol biosynthesis inhibitor includes morpholine fungicide, such as two
Methyl morpholine, benzamorph, carbamorph, dimethomorph, dodemorfe, butadiene morpholine, flumorph and tridemorph.It was found that can
The example for effectively antagonizing other fungicides of one or more domestomycetes include carboxin, iprodione, fenpiclonil, Fu Erbang,
Fenpiclonil, bacterium pellet, 8-hydroxyquinoline, Dithane A40, oxycarboxin, cyprodinil, Bravo, Fluoxastrobin, trifloxystrobin, Fu Mei
Double, fluazinam, kobam, carbendazim and benomyl.These fungicides can in the present invention with one or more azoles alcohol or
Ergosterol biosynthesis inhibitor is applied in combination.
In various embodiments, biocide is insecticide.The example of insecticide include pyrazoline, indazole, oxidation indazole,
Pyrazoline carboxanilides, pyridazine, oxadiazines, tricyclic pyridazine, tricyclic oxadiazines, tricyclic triazine, carbaminate, organic phosphate
(such as poisoning barnyard grass and DDVP with poison), fenvalerate, Fipronil and indoxacarb and its metabolin and its mixture.
The optional consisting of antifungals of biocide, such as include group below: benzimidazole;Substituted morpholine;Triazole,
It may include propiconazole, Tebuconazole, hexaconazole and other triazoles etc.;Diazole may include Prochloraz, phthalocyanine, quaternary ammonium compound, different
Thiazolinone, Guanoctine, dodine, di-2-ethylhexylphosphine oxide thiocyanates, o-phenyl phenol etc.;Tertiary amino oxides, such as alkyl-dimethyl
Base amine oxide;Fungicide containing iodine etc..Biocide can be selected from insecticide, such as synthetic pyrethroid (such as fluorine chlorine chrysanthemum
Ester, decis, Permethrin etc.) or imidacloprid group.Those skilled in the art will be appreciated that other suitable selections.Many is killed
Biological agent is all known to those skilled in the art, including is used for those of wood preservation or agricultural.
In various embodiments, one or more biocides include quaternary ammonium compound, boron compound, fluorinated compound
Object or pyrrole.
In various embodiments, quaternary ammonium compound is that benzene pricks ammonium salt or dimethyl didecyl ammonium salt.In various embodiments,
Quaternary ammonium compound is benzalkonium chloride or dimethyl didecyl ammonium chloride.In various embodiments, quaternary ammonium compound is didecyl two
Methyl carbonic acid ammonium or didecyldimethylammonium ammonium bicarbonate.
In one embodiment, pyrrole is propiconazole or Tebuconazole or combinations thereof.
In one embodiment, one or more biocides are the desinsection as Permethrin or Biphenthrin
Agent, or the fungicide as Bravo.
In one embodiment, the composition includes amine oxide or alkoxylated amine, can help to biocidal
Distribution of the agent in matrix (such as timber).
The biocide with low solubility can be used as micronized particle, as lotion or microemulsion in the composition
Or it is introduced as encapsulated or microencapsulation particle.In various embodiments, the composition includes subparticle biocidal
The microemulsion of agent, biocide or microencapsulation biocide.
Although being not intended to be bound by any particular theory, the inventor believes that in the method for the invention, making
Cause to precipitate when reducing the pH of the alkaline aqueous solution of the metal comprising soluble complexes form with carbon dioxide source, to generate gold
Belong to compound subparticle.In certain embodiments, the metal in alkaline aqueous solution is converted carbonate by carbon dioxide.Cause
Solution is mixed the pH that can reduce solution in various embodiments by this with carbon dioxide source, so as to metal carbonate subparticle
Precipitating.
In various embodiments, solution is mixed to the pH that can reduce solution with carbon dioxide source, so as to metal borate Asia
Microparticle precipitating.It include borate ion by its aqueous solution for precipitating subparticle in some this embodiments.It is some this
In kind of embodiment, metal carbonate subparticle and metal borate subparticle can precipitate and/or metal carbonate and
The subparticle of metal borate can precipitate.
Metal salt subparticle includes metal salt.It should be understood that a other metal salt subparticle may include other co-precipitation
Component.For example, in some embodiments, metal borate subparticle may include an other subparticle, and it includes metals
The metal carbonate of the co-precipitation of borate and a certain amount.
In some embodiments, the subparticle is made of metal salt or is substantially made of metal salt.For example,
In some embodiments, metal carbonate subparticle is made of metal carbonate or is substantially made of metal carbonate.?
In some embodiments, metal salt subparticle include based on the weight of the particle at least 75,80,85,90,95,97,98,99,
Or 100% metal salt.
Metal complex is soluble under the alkaline condition of alkaline solution, but in certain embodiments under neutral ph
It is unstable.Soluble metal complex compound is decomposable when reducing the pH of alkaline solution by mixing carbon dioxide source.Solvable gold
Belonging to complex compound can be decomposed by the carbon dioxide reaction provided with carbon dioxide source.For example, one of soluble metal complex compound or
Multiple ligands can as described herein and carbon dioxide reaction.
One or more ligands of soluble metal complex compound can be by the decomposition of soluble metal complex compound from soluble metal network
Close object release.Alternatively or in addition, the salt of one or more ligands of soluble metal complex compound can pass through soluble metal
The decomposition of complex compound generates.In certain embodiments, pass through one or more ligands of the decomposition release of soluble metal complex compound
For glycol.In certain embodiments, the salt of the one or more ligand generated by the decomposition of soluble metal complex compound is carbon
The carbonate of sour ammonium (ligand is ammonia) or amine (ligand is amine).This salt can pass through ammonia ligand or amine ligand and chemistry
The reaction of the carbon dioxide of calculation amount generates.
Without wishing to be bound by theory, inventor believes the one or more ligands discharged or passes through soluble metal
Its salt that the decomposition of complex compound generates can reduce or prevent the aggregation and/or sedimentation of subparticle.As such, one discharged
Or multiple ligands or its generated salt potentially act as deflocculant to stablize subparticle.
Although it is generally desirable to by cost minimization to which use must for formation soluble metal complex compound as described herein
The one or more ligands for the minimum stoichiometric amount wanted, but excessive ligand can be used in certain embodiments.Obviously, alkali
Property aqueous solution and/or its salt (such as by being generated with carbon dioxide reaction) in there are this excessive (or free or not
Coordination) ligand can also reduce or prevent aggregation and/or sedimentation of the subparticle in water-based composition.
Reaction can carry out under optimal conditions, be formed by subparticle to maximize.However, it is understood that certain
In embodiment, the water-based composition may include unreacted raw material, such as the undecomposed soluble metal complex compound of trace.
Alkaline aqueous solution is mixed with carbon dioxide source to carry out under vigorous agitation, although stirring in some embodiments
Need not be violent.Those skilled in the art stir required for being readily determined according to the property and processing conditions of reactant
Traverse degree.Vigorous agitation can be provided by mixer, ultrasonic treatment of high speed agitator, commonly referred to as Silverson etc..Agitation
It can be high shear agitation.
Carbon dioxide source provides carbon dioxide for aqueous solution.According to used source, carbon dioxide can be introduced directly into instead
In answering or original position generates.Any suitable carbon dioxide source can be used.In various embodiments, carbon dioxide source is titanium dioxide
Carbon gas wraps carbonated solution or potential carbon dioxide source.
Carbon dioxide gas under agitation can be mixed gas sparging by alkaline solution by (for example) with alkaline solution.
In various embodiments, carbon dioxide gas can be molten with alkalinity under stress in suitable reactor (such as high-pressure reactor)
Liquid mixing.In mixing under stress (i.e. under the pressure for being greater than atmospheric pressure, so that carbon dioxide is remained liquid condition)
In some embodiments carried out in the suitable reactor (such as high-pressure reactor), can also use liquid CO 2 as
Carbon dioxide source.
Wrapping carbonated solution can be saturated by carbon dioxide.Wrapping carbonated solution can be aqueous solution.This
Kind solution can be prepared at low temperature, to increase the amount for dissolving in the carbon dioxide in the solution.Preparation packet is carbonated
The method of solution will be apparent to those skilled in the art.
Potential carbon dioxide source includes that can (for example) decompose to provide the organic carbon of carbon dioxide at reaction conditions
Acid esters, such as ethylene carbonate or dimethyl carbonate.It, can will be anti-in order to increase the rate that organic carbonate is decomposed into carbon dioxide
Mixture is answered to heat.
Carbon dioxide source can be mixed with controllable rate with solution, such as slowly be mixed with solution, to obtain desired pH.It can
PH is monitored during mixing step.
Solution can be mixed with carbon dioxide source at any suitable temperature (such as from 0 to 80 DEG C temperature), with drop
The pH of low alkalinity solution, so as to metal salt subparticle precipitating.Advantageously, it can sink at ambient temperature in certain embodiments
It forms sediment.
Solution is mixed to the pH that can reduce solution with carbon dioxide source, so as to metal carbonate subparticle precipitating.
Alkaline aqueous solution can further include the source of one or more acid, such as the source of one or more weak acid.?
In some embodiments, can before forming soluble metal complex compound, in the process or rear one or more acid are introduced into solution
Source, such as the source of one or more weak acid, as long as one or more acid will not interfere soluble metal complex compound
It is formed or decomposes soluble metal complex compound.In certain embodiments, can mix one or more optional dispersing agents it
Before, mix one or more acid in the process or later.In some embodiments, before the one or more sour and alkalinity
The mixing of body aqueous solution.
In some embodiments, the method may include in any order by solution, carbon dioxide source and a kind of or more
The source mixing of kind acid.One or more acid can be weak acid.Weak acid is the acid that only can partially dissociate in aqueous solution.
I.e. only some weak acid can discharge its proton in the solution.In contrast, strong acid can then will be completely dissociated in aqueous solution.Acid
Acid ionization constant (Ka) shows the degree that acid dissociates in the solution.Acid ionization constant can be expressed as pKa.Weak acid, which can be, to be had extremely
The weak acid of few about 6 pKa.Weak acid can be the weak acid that salt essentially insoluble in the water of pH7 can be formed in metal.Ying Li
It solves, the subparticle formed in this embodiment of the method may include the metal salt of weak acid.
The example of weak acid includes but is not limited to boric acid and phenol, such as o-phenyl phenol, phenol, cresols, xylenol, hundred
In fragrant phenol etc..Weak acid source is boric acid or borate, such as borax in certain exemplary embodiments.
The metal salt precipitated in the method is substantially insoluble in.Metal salt can have molten less than 0.1g/L and 20 DEG C
Xie Du.Metal salt preferably has less than 20 DEG C of 0.01g/L of solubility.
For example, being used to that timber or the biocide of plant is protected once to apply usually has low solubility.Otherwise work as exposure
They can be lost in environment when being exposed to water (such as rainwater).Certain this biocides there is low solubility but be enough by
The intake such as insect, fungi.Example includes that Ksp (solubility product in water) is 1.4 × 10–10Copper carbonate, Ksp be 1.4 × 10–11's
Zinc carbonate and Ksp are 2.2 × 10–20Kocide SD.
In the case where the composition includes metal carbonate subparticle, the method can further include will be described
Composition alkali process, to convert metal hydroxides subparticle for metal carbonate particles.Converting the alkali used can
To be alkali or alkaline earth metal hydroxide.Reaction can be carried out advantageously at ambient temperature.
In the case where the composition includes the subparticle of metal carbonate or metal hydroxides, the method can
It further includes and heats the composition, to convert metal oxygen for metal carbonate particles or metal hydroxide particle
Compound subparticle.The composition can heat at any suitable temperature, such as from about 50 to about 95 DEG C of temperature.At certain
In a little exemplary embodiments, the composition about 80 DEG C at a temperature of heat.
The method can further include the water-based composition of the subparticle generated when being included in the pH for reducing solution
With one or more dispersing agents or other dispersing agent and/or one or more surfactants or other surface-active
Agent mixing, to increase the stability of subparticle in the composition, such as the stability to sedimentation and/or cohesion.
According to the target application of the composition, the method be can further include by mixing one or more acid or alkali
(such as weak acid or weak base) adjusts the pH of the composition comprising subparticle.Mixed acid or alkali may act as pH buffer.
In some embodiments, pH is adjusted by mixing one or more acid and one or more alkali.
In certain embodiments, the pH of the composition can be adjusted by mixing boric acid and/or borate (such as borax).
In some embodiments, adding borate (such as after forming precipitating) can produce the combination containing free borate ion
Object.Therefore in some embodiments, water-based composition includes borate ion.
As described in each example, inventor's discovery uses borax as buffer, and the pH of the composition can be adjusted to
About pH9.Sodium tetraborate (borax) or corrosion inhibitor, therefore the corrosiveness of the composition can be reduced.
It is about 6 to about 10 that the pH of the composition, which can be adjusted to pH,.In some embodiments, the water-based composition
It is about 7.5 to about 9.5, for example, about 8 to 9 that pH, which can be adjusted to final pH,.PH can be monitored (simultaneously in the pH adjustment process
And can be monitored in any other step as described herein that pH is changed).The appropriate method of pH is monitored for this field
It is known for technical staff.
In some embodiments, the pH of alkaline solution be reduced to a certain pH (such as pH is about 7.5 to 9.5, for example, about 8 to
9), so as to metal salt subparticle precipitating, to form the water-based composition of this pH, it includes have to be suitble to target application
The subparticle of pH.In such an embodiment, no subsequent pH adjustment step may be necessary.
Without wishing to be bound by theory, inventor believes at the pH from about 7.5 to about 9.5 (for example, about from 8 to 9),
The solubility of the metal salt (such as copper carbonate) precipitated is low.In addition, inventor believes the corruption of the composition at this pH
Erosion effect is also low, this is because the ionic metal in solution is seldom.This pH may further be used to reduce or minimize metal (such as
Copper) from the leaching and/or loss of the matrix (such as timber and other lignocellulosic matrixes) through the compositions-treated.
It for example, in certain embodiments, the composition can have the pH from about 8 to 9, and include basic copper carbonate form
Mantoquita subparticle.
Inventors have found that at least can have low corruption by the water-based composition that the method generates in certain embodiments
Erosion effect.In various embodiments, when being tested using AWPAE12 Corrosion standards method, the composition is compared with standard ACQ
At least low 20% mpy can be generated.Although AWPAE12 Corrosion standards method may not specify the amount for being added to the copper of timber,
But those skilled in the art will be appreciated that typical introduction volume, and also it will be appreciated that higher loading capacity can proportionally make to corrode
Deteriorate.Any suitable standard ACQ can be used to compare.In some embodiments, standard ACQ is A type, Type B, c-type or D
Type.It is compared in certain preferred embodiments with Type B ACQ.
Alkaline aqueous solution includes metal, one or more can form soluble complexes with metal under alkaline condition and match
Body and optional one or more dispersing agents.Although the presence of one or more dispersing agents can be used in some embodiments
Stablize and be formed by subparticle, but inventor's discovery at least presence of one or more dispersing agents in some embodiments is not
It is necessary.Without wishing to be bound by theory, inventor believe be formed by subparticle in such an embodiment can be by such as
Other components present in composition as described herein are stabilized without assembling and/or settling.
Can by provide comprising metal and it is one or more under alkaline condition can with metal formed soluble complexes
The alkaline precursor aqueous solution of ligand, and one or more dispersing agents are optionally mixed, to provide alkaline aqueous solution.In certain realities
It applies in example, two or more different dispersing agents can concurrently or consecutively be mixed with precursor solution.
Alkaline aqueous solution can further include one or more surfactants.One or more surfactants can
It is mixed before or during optionally mixed dispersant with precursor solution, or is optionally mixing one or more dispersing agents
It is mixed later with alkaline solution.
The pH of alkaline solution or precursor solution can be adjusted when required by mixed acid or alkali, such as optionally mixed
Before dispersing agent or before mixing carbon dioxide source.
Alkaline solution and precursor solution also may include one or more organic solvents as described herein.
Alkaline solution comprising soluble metal complex compound can have at least 9 pH, for example, at least 9.5,10,10.5,11,
11.5,12,12.5,13,13.5 or 14, and useful range can be selected from any two in those values.Basicity can be by alkali hydrogen
Oxide, ammonia or amine contribution.
The pH of alkaline solution is lowered in the method, so as to metal salt subparticle precipitating.The pH of alkaline solution can
Being reduced to pH is 4.5 to about 10, for example, about 4.5 to about 9, for example, about 5 to 9,5.5 to 9,6 to 9,6.5 to 9 or 7 to 9.At certain
In a little embodiments, it is about 6 to about 9 that the pH of alkaline solution, which is reduced to pH,.In other embodiments, the pH of alkaline solution can be reduced to
PH is about 6 to about 10, for example, about 7.5 to 9.5.In certain exemplary embodiments, it is about 8 that the pH of alkaline solution, which is reduced to pH,
To 9.
In certain embodiments, the method includes that metal salt subparticle is deposited to matrix (example from alkaline aqueous solution
Such as the particle of carbon, silica or clay, it is also possible to subparticle) on.
Alkaline aqueous solution or precursor solution can by the aqueous alkalescence medium comprising alkali by source metal and a kind of or more
Kind can form the ligand reaction of soluble complexes with metal to prepare under alkaline condition.Reaction can be at any suitable temperature
It carries out, such as 5 to 95 DEG C, 10 to 90 DEG C or 20 to 50 DEG C.Advantageously, in various embodiments, reaction can be at ambient temperature
It carries out.
Being formed by soluble complexes can be-two alcohol complex of metal, metal-ammonia complex or metal-amine complexing
Object.The ligand for forming this soluble complexes includes but is not limited to ammonia, amine and glycol, such as dihydric alcohol, trihydroxylic alcohol and more
First alcohol.
The alkali for providing the alkaline condition for forming soluble complexes can be alkali metal hydroxide (such as sodium hydroxide or hydrogen
Potassium oxide), ammonia or amine.When ligand is ammonia or amine, the ligand can also serve as alkali in the reaction.
It can be metallic compound or metal element with the source metal of one or more ligand reactions.Source metal is usually solid
Body is dissolved with when one or more ligand reactions under alkaline condition.Metallic compound can be metal salt, such as carbonic acid
Copper, Kocide SD, copper oxide, zinc carbonate, zinc hydroxide or zinc oxide.In another example, metal salt can be boric acid
Copper.Metal element can be elemental copper, (for example) react with ammonia and carbonate is reacted with oxygen (or oxygen in air)
When dissolve.
Various metals (such as metal of First Transition series) are capable of forming metal-ligand network as known to those skilled in the art
Close object.
The metal complex formed in method of the invention can be metal-ammonia complex or metal-amine complex.In gold
In category-ammino-complex, metal and at least one ammonia (or ammonate) ligand complex.For example, cuprammonium is with formula Cu (NH3)4 2+
Copper-ammino-complex.The charge 2+ of the complex compound is by one or more suitable anion balances, such as by carbonate anion
Balance obtains carbonic acid cuprammonium, or is balanced to obtain boric acid cuprammonium by borate.Carbonic acid cuprammonium is cationic octahedral complex.Gold
The other examples of category-ammino-complex include Co (NH3)4、Zn(NH3)6With Ni (NH3)6。
The metal of many First Transition series forms tetrammine.The metal of second, third and the 4th transition series can
Form similar compound.It is some to will form alternative complex compound, such as silver, it will form two ammino-complexes.Copper and mickel can
(for example) form hexmmine.
The subparticle dispersion of the salt of these metals or its oxide or hydroxide can be used for each as described herein
Kind application.In certain embodiments, method of the invention provides the advantageous manner for obtaining this dispersion.
In certain embodiments, metal complex is copper tetrammine;Cu(NH3)4 2+.The metal in this complex compound
It there may come a time when with the chemical ratio of ligand critically important to solubility.For example, Cu (NH3)4 2+With high-dissolvability, and Cu (NH3)2 2+Then
Do not have.Similarly, Ag (NH3)2 2+With high-dissolvability, and Ag (NH3)2+Do not have then.
In the embodiment of the present invention method, the stoichiometric ratio of ligand and metal, which to be formed by complex compound, to be dissolved in
In alkaline aqueous solution.In some embodiments that wherein metal is copper, copper: ammonia stoichiometric ratio can be about 1:4.In some realities
It applies in example, it will during the carbon dioxide and ligand reaction formation metal salt subparticle by providing carbon dioxide source
The ratio of metal and ammonia ligand changes.It should be understood that this high-caliber ammonia can lead to when the ratio of copper and ammonia ligand is 1:4
PH is got higher.When controlledly adding carbon dioxide, pH is lowered, and ammino-complex decomposes, and forms submicron particles.
In metal-amine complex, metal and at least one amine are complexed.The example of suitable amine includes but is not limited to single
Ethanol amine, diethanol amine, triethanolamine, ethylenediamine etc..
Metal can change with the stoichiometric ratio of amine or ammonia according to the ratcheting degree of metal and amine.For example, as ethylenediamine this
The bidentate ligand of sample can occupy two co-ordination positions of metal.In various embodiments, the stoichiometric ratio of metal and ammonia or amine
For at least about 1:1 to 1:6.In certain exemplary embodiments, the stoichiometric ratio of metal and ammonia is at least 1:4.
In various embodiments, alkaline solution and/or precursor solution include metal ammine complex or metal amine complexes,
The ammonia or amine of middle complex compound are provided by ammonia or amine, wherein pH be at least 9, for example, at least 9.5,10,10.5,11,11.5,12,
12.5,13,13.5 or 14, and useful range can be selected from any two in these values.
Ammonia metal complex or amine metal complex can be prepared by reacting metal salt with ammonia or amine, be formed octahedra
Complex compound.In one embodiment, metallic compound and ammonia or amine understand self alkalization (such as ammonia), form ammino-complex or amine
Complex compound.Prepare ammonia metal complex or amine metal complex other methods will be to those skilled in the art it is aobvious and
It is clear to.
Metal complex can be-two alcohol complex of metal, this complex compound be metal and one or more glycol (such as
1,2 glycol, such as glycerol or 1,3 glycol, such as 1,3 propylene glycol) complex compound.- two alcohol complex of metal herein may be used
Referred to as metal glycol compound.
The preparation of-two alcohol complex alkaline solution of metal is PCT/IB2012/053836 (being published as WO2013/014644)
In be described, entire content is incorporated herein by reference.
In certain exemplary embodiments, metal complex is-two alcohol complex of copper.In some embodiments, copper-two
Alcohol complex (or copper glycol compound) is the anionic species comprising copper, and shape is complexed by one or more glycol at a high ph in copper
At soluble copper complex, generally there is charge 2-.
Glycol includes that at least two hydroxyls to form glycol compound can be reacted with copper material.Increased using alkali compounds
PH will form copper 2- complex compound.Charge 2- can be by any suitable cation balance.
In one embodiment, glycol is dihydric alcohol, trihydroxylic alcohol or polyalcohol.In one embodiment, at least two hydroxyl
Base is the 1,2- relationship (i.e. adjacent) or 1,3- relationship for being capable of forming-two alcohol complex of metal relative to each other.Suitable glycol
Example include but is not limited to ethylene glycol, propylene glycol and glycerol.
In one embodiment, glycol be dihydric alcohol, trihydroxylic alcohol or polyalcohol, or mixtures thereof.In one embodiment
In, dihydric alcohol, trihydroxylic alcohol or polyalcohol are C2-C20Alcohol.In one embodiment, C2-C20Alcohol is C2-C6Dihydric alcohol, trihydroxylic alcohol,
Or polyalcohol, polymeric alcohol, or mixtures thereof.
In one embodiment, polymeric alcohol is one or more C2-C6The polyethers of dihydric alcohol, trihydroxylic alcohol or polyalcohol polymerize
Object.In one embodiment, glycol C2-C6Dihydric alcohol, trihydroxylic alcohol or polyalcohol or the polyethers of one or more of them are poly-
Close object.
In one embodiment, C2-C6Dihydric alcohol, trihydroxylic alcohol or polyalcohol are that low-grade alkylidene or lower alkenylene are sweet
Alcohol.In one embodiment, C2-C6Dihydric alcohol, trihydroxylic alcohol or polyalcohol are low-grade alkylidene glycol.In one embodiment,
C2-C6Dihydric alcohol, trihydroxylic alcohol or polyalcohol are low-grade alkylidene glycol or triol.In one embodiment, glycol be selected from by with
The group of lower composition: ethylene glycol, propylene glycol, glycerol, or mixtures thereof.In one embodiment, glycol is selected from and is made up of
Group: ethylene glycol, glycerol, or mixtures thereof.
In one embodiment, glycol is vicinal diamines.In another embodiment, glycol is polyol.One
In a embodiment, glycol is sugar or polyalcohol.
Many glycol are commercially available.
In one embodiment, glycol is selected from the group being made up of: ethylene glycol, propylene glycol, glycerol and its mixing
Object.In another embodiment, glycol be ethylene glycol, glycerol, or mixtures thereof.In one embodiment, glycol is ethylene glycol.
In another embodiment, glycol is glycerol.
In one embodiment ,-two alcohol complex of metal is formula (I) compound:
Wherein the complex compound generally has 2 negative electrical charges;Wherein R1And R2It is each independently selected from and is made up of
Group: hydrogen, hydroxymethyl, alkyl, alkoxy, substituted carboxyl etc..
In one embodiment, R1And R2Respectively hydrogen, the compound are copper (II) ethylene glycol complex compound (with two second
The copper (II) of glycol ligand connection).
In another embodiment, R1And R2Respectively methylol, the compound are copper (II) glyceride.
It will be understood by those skilled in the art that when (for example) there is highly basic, formula (I) compound can be had when in the solution
Charge (charge is not shown).Charge can be by the way that with necessary chemical ratio, there are any suitable counter ion balances.For example, working as formula
(I) when compound has charge -2, anionic charge can be put down by the way that there are a bivalent cations or two univalent cations
Weighing apparatus.In one embodiment, counter ion is sodium cation.
Field of coordinative chemistry it should be understood to the one skilled in the art that transition metal can form coordination network in the presence of suitable ligand
Close object.For example, copper is capable of forming octahedral coordination complex compound, observed such as in example as described herein is typical dark blue
Color.
The example of octahedra copper glycol co-ordination complex is described below.Two alcohol complex of copper is in copper atom and two
There are four keys for tool between the oxygen atom of glycol ligand, therefore two other ligands may participate in form the octahedral complex.
Suitable other ligand includes (for example) water (as shown below), ammonia (ammonate), amine, alcohol, organic acid, bidentate ligand (example
Such as ethylenediamine) or other suitable molecules.The copper complex is generally had 2 negative electrical charges and (is not shown in flowering structure
Show), thus in high pH medium have dissolubility and/or with alkali metal forming salt.
Without wishing to be bound by theory, inventor believes that the copper diol compound prepared in following example 1 includes
Na2CuC6H12O6.2H2O。
Those skilled in the art will be appreciated that in addition the complex compound of example 2 is also referred to copper bis ethane -1,2- glycol and closes two hydrations
Copper (II) disodium salt.Similarly, if using glycerol as glycol as in other examples, the complex compound can
Referred to as 3- hydroxyl propyl- 1,2- glycol close, two hydrations copper (II), disodium salt.
Although term glycol compound can be used in this document to describe this compound, but it is clear that this complex compound is not
It is the metal salt of glycolic.In-two alcohol complex of metal, each in one or more glycol includes two or more
A hydroxyl, oxygen atom and metal complex.One or more glycol are free of carboxylic acid.
It will be understood by those skilled in the art that different metallicses can accommodate the ligand of different number.The oxygen of metallics
The quantity of the open ended ligand of the substance may be will affect by changing state.
The property of the oxidation state and ligand (including glycol ligand) of metallics determines total electricity of-two alcohol complex of metal
Lotus.Charge can be as with any suitable cation or (if applicable) anion balance existing for necessary chemical ratio.Sun
The example of ion includes metal cation, such as alkali or alkaline earth metal cation, for example, lithium, sodium, potassium, magnesium and calcium sun from
Son.The example of anion includes inorganic anion, for example, halide anion (such as fluorine, chlorine, bromine and iodine anion), sulfate radical,
Phosphate radical, hydroxyl, nitrate anion, carbonate and heavy carbonic root anion and organic anion, such as alkoxy, acetate
And carboxylate radical.Those skilled in the art should be familiar with other cations and anion.
- two alcohol complex of metal includes at least one glycol.In one embodiment ,-two alcohol complex of metal includes two
A glycol ligand.In another embodiment, glycol compound includes three glycol ligands.
- two alcohol complex of metal can further include one or more non-glycol ligands.In one embodiment, metal-
Two alcohol complexs include one or more water ligands.In another embodiment ,-two alcohol complex of metal includes one or more
Alcohol ligand.In another embodiment ,-two alcohol complex of metal includes one or more ammonia ligands or amine ligand.In a reality
It applies in example ,-two alcohol complex of metal includes one or more ligands selected from water, alcohol, ammonia, amine and its mixture.
Sometimes preferably with the mixture of ligand.In one embodiment, this ligand may include with ammonia, amine and/or
The mixed glycol of water.In one embodiment, this ligand may include the glycol mixed with ammonia and/or amine.In another implementation
In example, this ligand may include the glycol mixed with water.The example of suitable amine includes but is not limited to monoethanolamine, diethanol
Amine, triethanolamine, ethylenediamine etc..
In some embodiments, the stoichiometric ratio of glycol and metal (such as copper) is about 1:1 to about 3:1, about 1:1 to 2:
1 or about 2:1.
In various embodiments ,-two alcohol complex of metal reacts shape by glycol under alkaline condition and metallics
At wherein the glycol is one of ethylene glycol, propylene glycol or glycerol or a variety of.In another embodiment, use is other
Glycol.
In certain embodiments, alkaline solution and/or precursor solution include the copper glyceride in water-based liquid medium,
Described in the pH of composition be at least about 11, such as 11.5,12,12.5,13,13.5 or 14, useful range can be selected from those
Range in value between any two.
As being referred to herein, composition, solution, dispersion, term " aqueous " refers to used in colloid or other liquid
The composition, solution, dispersion, colloid or other liquid are by the composition, solution, dispersion, colloid or liquid
Poidometer includes at least 10% water, the preferably water of at least 15,20,25 or 30% by weight.
Therefore the alkaline aqueous solution comprising subparticle and/or precursor aqueous solution and/or water-based composition may include by group
Close object poidometer about 10 to 99.5% amount water, such as based on the weight of composition about 10 to 99.5,15 to 99.5,20 to
99.5,25 to 99.5,30 to 99.5,35 to 99.5,40 to 99.5,45 to 99.5,50 to 99.5,60 to 99.5,70 to 99.5,
80 to 99.5 or 90 to 99.5%.
Alkaline solution and/or precursor solution and/or water-based composition comprising subparticle can further include it is a kind of or
A variety of organic solvents.One or more organic solvents can be alcohol, ketone, lactams, glycol ethers or wherein any two kinds
Or more combination.In one embodiment, the alcohol is C1-C6Alcohol.In one embodiment, the alcohol is selected from methanol, second
Alcohol, normal propyl alcohol, isopropanol, n-butanol, sec-butyl alcohol, isobutanol, the tert-butyl alcohol and its mixture.In one embodiment, the alcohol
Selected from methanol, ethyl alcohol, normal propyl alcohol, isopropanol and its mixture.In one embodiment, the alcohol is selected from the group being made up of
Group: methanol, ethyl alcohol and its mixture.In one embodiment, the alcohol is methanol.In another embodiment, the alcohol is
Ethyl alcohol.
In various embodiments, comprising by its subparticle formed alkaline aqueous solution and/or precursor aqueous solution and/or
Or mixtures thereof aqueous and one or more simple alcohols of water-based composition packet (such as C1-6 alcohol).
The alkaline solution or precursor solution can further include the mixture of glycol or glycol (such as in soluble metal network
When conjunction object is-two alcohol complex of metal).
- two alcohol complex of metal can form-two alcohol complex of metal by the preparation of reacting of metal salt and glycol.One
In a embodiment, metallics and glycol are reacted in the presence of alkali (such as sodium hydroxide or potassium hydroxide), form network
Close object.Those skilled in the art should be familiar with preparing other methods of-two alcohol complex of metal.
In various embodiments, the method can generate free diol, and the glycol can be recycled.
In various embodiments, the method can generate ammonium carbonate, and the ammonium carbonate can be recycled.
On the other hand, the present invention relates to the combinations prepared by the method for the present invention comprising metal salt subparticle
Object.
On the other hand, the present invention relates to a kind of method for handling matrix, the method includes to pass through to matrix application
Composition prepared according to the methods of the invention comprising metal salt subparticle.
Composition comprising subparticle can be water-based composition as described herein comprising subparticle.Favorably
Ground, the water-based composition can be colloidal dispersion form, be suitble to handle lignocellulosic matrix, such as timber.
On the other hand, the present invention relates to the matrixes handled according to the method for the present invention.
Described matrix can be organic matrix.In one embodiment, the organic matrix is lignocellulosic.At one
In embodiment, the lignocellulosic matrix is timber or wood composites.In one embodiment, the organic matrix is wood
Material.
In one embodiment, the timber sufficiently dry, to allow to be impregnated by the composition.In one embodiment
In, described matrix is the timber at or below fibre saturated point.
In certain embodiments, composition of the invention can provide extensive range when providing biocide for matrix,
And alleviate the health problem using volatile ammonia or the cost using amine.
Composition of the invention can be used to assign various characteristics for matrix, including biocidal protection or pigmentation.This hair
The those of ordinary skill in the bright field being related to, which unquestionably should be appreciated that, can be applied to various compositions of the invention.
By way of example, the processing infected in the infection of harmful organism organism or in advance prevents when being desired,
The composition with remove the evil characteristic (such as fungicidal properties, bactericidal characteristic, insecticidal properties) or preservative characteristic can be used
(Biocidal composition).
The composition may include for making water-proofing treatment to matrix or providing the compound of flame-retarding characteristic.Handle compound
The combination of (such as biocide and fire retardant) will obviously provide beneficial characteristics for matrix.The composition may include inorganic pigment
Dispersion is to change the color of matrix.
Although being not intended to be fettered, biocide can include: copper, zinc, cobalt, boron, quaternary ammonium compound, organic iodate
Close object, triazole, boron compound, insecticide (such as synthetic pyrethroid etc.) or these mixture.
Fire retardant may include phosphorus-containing compound, guanidine compound, melamine compound, boron compound or these mixing
Object.In some cases, the composition include addition emulsifier or surfactant when can be used biocide and/or
Fire retardant prepares lotion in solvent combination.
As used herein, " matrix " should refer to any material that can need to deliver composition of the invention;For example,
Processing intent is or raw by harmful organism to protect matrix from harmful organism organism on matrix or base intracorporal growth
Object removes on matrix or in matrix, perhaps prevent harmful organism organism on matrix or base tumor growth or alleviate
Harmful organism organism is on matrix or base tumor growth.This matrix can be lignocellulosic, such as tree living, wooden
Product, timber or log.The present invention can be applied over the matrix or essentially dry matrix of the moisture containing certain level, place
In or lower than fibre saturated point.The present invention can be applied over inorganic matrix, such as concrete or metal.
Although specification, which specifically focuses on, delivers the composition to timber, plant, leather, painting layer etc., it should be understood that
The method can be applied over other matrixes.
At least in the case where lignocellulosic matrix, those of " essentially dry " includes drying by conventional method
Timber.Weight ratio of moisture of this timber containing about 1 to about 30 percentage as dry weight of wood, although some
In the case of moisture content can be higher.Essentially dry lignocellulosic matrix includes timber, and it is true to have passed through kilning, RF
The processing such as sky is dry may be grated as final products or near-final product, and may include that (for example) timber is multiple
Condensation material.
" harmful organism " or " harmful organism organism " as mentioned in this article may include can infect organic matrix (such as wood
Material) any organism.Although the present invention can especially be applied over fungi, harmful organism organism may also include insect etc..
Fungi and harmful organism will be apparent to those skilled in the art.
As used herein, term " processing (treatment) " should take it most wide in the case where handling matrix
Meaning in general range.It should not be construed as showing that matrix is treated as harmful organism organism and is completely removed, although one
This in a little embodiments is preferred.The growth of harmful organism organism prevents (such as preventative process) and improvement also by term
" processing (treatment) " includes.The relational language as " processing (treating) " etc. should understand in an identical manner.
Subparticle composition can be used by any known mode of composition and material be applied to matrix surface or
It is applied to intrinsic silicon.By way of example, the composition by dipping, spray, spraying or brushes application.
Although inventor is not considered as that active pressure must be applied by delivering composition according to the present invention, may be present actively
Pressure system (positive pressure or vacuum) can be used to help the case where delivering.It can refer to WO2004/ by way of example in this regard
Delivery system described in 054765, is incorporated herein by reference in their entirety.
Although the operation temperature for applying the composition is suitble to (or biocidal can be helped according to subparticle, biocide
Agent) (if present) and the composition other components property (such as its solubility etc.) and change, but institute
Stating composition can at ambient temperature or about apply at ambient temperature.It can be used up to according to the component of the composition
100 DEG C of temperature.But higher temperature will increase energy consumption.
As discussed herein above, method of the invention can be applied to essentially dry (be saturated at or below fiber
Point) matrix.In one embodiment, the composition is applied to the matrix at or below fibre saturated point.
It the content of subparticle can select in amount to used composition and/or composition, to provide expectation
Horizontal processing.
In some embodiments, composition of the invention is used to that organic matrix is impregnated or inculcated with metal salt.
In many countries, for timber, there are various processing standards (such as NZ3640), provide preservative and penetrate into timber
In and for each danger classes retain given level preservative requirement.Risk class or danger classes are higher, need
Retention level it is bigger.For ACQ- type preservative, the reservation of copper is for H3.2, H4 and H5 timber typically respectively about 0.22%
M/m, 0.7%m/m and 0.9%m/m.Advantageously, in some embodiments, composition of the invention is used to provide with similar
The timber of the reservation of biocide.
In other embodiments, composition of the invention is applied to organic matrix surface as preventative process.
As discussed herein above, the method is optionally including pH adjustment step, to apply by the composition
The pH of the composition comprising metal salt subparticle is increased or decreased before to organic matrix.
Composition of the invention can easily be applied to plant living by method in extensive range, such as by impregnating,
Spraying is easily applied to plant living by soil application.
Inventors have found that method of the invention can be used to prepare aqueous subparticle Biocidal composition, for heavy
Drop and/or cohesion are stable, and it is readily dispersed in water.Current biocide technology is set without using expensive
Standby, a large amount of energy cannot provide this simple finely ground particle substance in the case where using expensive solvent.Side of the invention
Simple processing technique can be used to carry out for method, and without excessive Capital expenditure, also not need what wet milling techniques were usually directed to
High energy.The method can also reduce the demand of the solvent for high-content, surfactant etc., and otherwise it will increase into
This is without will increase biological property.
Example
Following non-limiting example is provided to illustrate the present invention, but is in no way intended to limit its range.
Example 1
Into a reaction vessel, addition is equivalent to 1.1g (0.005mol) basic copper carbonate of 0.01mol copper.Thereto
Addition 1.9g (0.02mol) glycerol adds 20ml water, obtains the opaque suspension of light green color.It is slowly added 0.4g under agitation
(0.01mol) sodium hydroxide, until all basic copper carbonates all be dissolved, obtain a dark blue solution.Copper material is as copper
Glyceride (i.e. copper-glycerol complex compound) exists.
0.3g polyacrylic acid dipersant in water is added thereto.The dispersing agent is Orotan 731DP.Mixture is stirred
It is dynamic, generate a clear solution.
Arbon dioxide solution is added into clear solution under vigorous agitation.As pH is reduced, insoluble basic carbonate
Copper is precipitated from solution, obtains the transparent light green solution of a subparticle dispersion.The dispersion is at least one moon
Interior holding is stablized, and does not observe sedimentation or cohesion.
In order to which determination has formed subparticle dispersion, a certain amount is placed in clear, colorless container.Pass through container
When dispersion is observed, visually see it being fully transparent (as shown in Figure 1).But when the arrow beam of light of LED based light source irradiates
When by the fluid, the region that light passes through is in muddy (as shown in Figure 2).This observation result of Tyndall effect determines
Generate colloidal state or subparticle dispersion.
Use the Mastersizer 2000Ver.5.60 from England Malvern Malvern Instruments Ltd
The particle size distribution of composition sample is tested.Particle size distribution is shown in Figure 3.Obviously, the particle of preparation exists
In the range of 100nm to 400nm.It is shown as the artefact that the distribution of particles from 2 to 30um is considered as test method.
Example 2
The colloidal dispersion that basic copper carbonate is prepared according to the step identical as described in example 1, in addition to glycerol is counted by chemistry
The ethylene glycol substitution of equivalent is calculated (to form copper-ethylene glycol complex compound or copper ethylene glycol compound, rather than copper glyceride or copper-
Glycerol complex compound).
Example 3
Copper glyceride solution is prepared according to the step of described in example 1.0.3g polyacrylate in water is added thereto
Dispersing agent.The dispersing agent is Orotan 731DP.The mixture is stirred, a clear solution is generated.
Carbon dioxide gas is bubbled by the clear solution, until pH is brought down below 10.This generates basic copper carbonate
Transparent subparticle dispersion.With equally prove that there are colloidal dispersions using light beam (observe Tyndall effect) in example 1
Body.
Example 4
Copper glyceride solution is prepared according to the step of described in example 1.The polyacrylic acid of 0.3g in water is added thereto
Dipersant.The dispersing agent is Orotan 731DP.The mixture is stirred, a clear solution is generated.
Carbon dioxide gas is bubbled by the clear solution, until pH is down to 9.This generates the saturating of basic copper carbonate
Bright subparticle dispersion.With in example 1 equally using light beam prove there are colloidal dispersions.
Example 5
Copper glyceride solution is prepared according to the step of described in example 1.The polyacrylic acid of 0.1g in water is added thereto
Dipersant.The dispersing agent is Orotan 731DP.Mixture is stirred, a transparent fluid is generated.
Carbon dioxide gas is bubbled by the clear solution, until pH is down to 10.This generates basic copper carbonates
Transparent subparticle dispersion.With in example 1 equally using light beam prove there are colloidal dispersions.
Example 6
Into a reaction vessel, addition is equivalent to 1.1g (0.005mol) basic copper carbonate of 0.01mol copper.Thereto
Addition 1.9g (0.02mol) glycerol adds 2ml water, obtains the opaque suspension of light green color.0.3g Orotan is added thereto
731DP.Be slowly added 0.4g (0.01mol) sodium hydroxide under agitation, until all basic copper carbonates all be dissolved, generate one
A dark blue solution.Copper material exists as copper glyceride.
The water that 140ml is saturated at 10 DEG C by carbon dioxide is added into the solution.This generates basic copper carbonate colloidal state
Dispersion.PH is 10.
Example 7
1.1g (0.005mol) the basic copper carbonate preparation of 0.01mol copper is equivalent to by adding into a reaction vessel
Carbonic acid cuoxam.0.4g (0.005mol) ammonium carbonate is added together with 20ml water.0.3g Orotan 731DP is stirred to this
In solution.Be slowly added ammonia solution (S.G.0.880) under agitation, until basic copper carbonate is completely dissolved, obtain one it is non-
Often dark blue solution.
The water being saturated at 10 DEG C by carbon dioxide is added under vigorous agitation, until pH is 7.This generates transparent light blue
Basic copper carbonate subparticle dispersion.
The dissolution of copper carbonate can be improved including ammonium carbonate, but is not necessary.
The scanning electron micrograph of dispersion granule is shown in FIG. 4.The 2um scale in the lower right corner is divided into 10
200nm increment.As can be seen that particle size is about 200nm.
Example 8
The basic copper carbonate dispersion samples prepared in example 5 are heated to 80 DEG C, carry out 10 minutes periods.Dispersion
It deepens as dark brown color.This is copper oxide disperses body.
Example 9
The sample of the basic copper carbonate dispersion prepared in example 7 is tested in corrosion research.By two mild steel
Metal testing plate is placed in the dispersion of certain volume.There is no signs of corrosion in steel test piece after 7 days.
In general, by corroding in the displacement to test piece of the copper of solution, this passes through the deposition or on the metal surface of copper
The various oxides of copper and/or iron are formed to recognize.Steel test piece keeps bright and bright, shows not replace.
The further research for comparing general AC Q and composition of the invention is carried out.It is prepared for copper concentration phase
Same solution adds steel test piece, and visual monitoring.In 4 days, the test piece for being exposed to ACQ shows corrosion and black deposit
Formation, appearance changes completely.The test piece for being exposed to composition of the invention keeps bright and bright after 5 weeks.
Example 10
Prepare carbonic acid cuoxam according to the step of described in example 7, in addition to a kind of 0.15g Corolan OT (naphthalene sulphur
Sour formaldehyde condensation products) 0.15g Orotan 731DP is added together, rather than add 0.3g Orotan 731DP.
Sample is purged with carbon dioxide gas under vigorous agitation.This generates transparent basic copper carbonate subparticles point
Granular media.
Example 11
Prepare carbonic acid cuoxam according to the step of described in example 7, in addition to a kind of 0.15g Corolan OT (naphthalene sulphur
Sour formaldehyde condensation products) 0.15g Orotan 731DP is added together, rather than add 0.3g Orotan 731DP.
0.1g surfactant-dispersed agent neopelex is added before adding carbon dioxide.
Then sample is purged with carbon dioxide gas under vigorous agitation.This generates transparent basic copper carbonate sub-micros
Grain dispersion.
Example 12
Prepare zinc carbonate colloidal dispersion.0.01mol zinc oxide is added into 20ml water.0.01mol carbon is added thereto
The ammonia (0.85g) plus 0.3g Orotan 731DP of sour hydrogen ammonium (0.79g) plus 30% aqueous solution form of 0.05mol, generate one
Transparent colourless solution.
The water being saturated by carbon dioxide is added under vigorous agitation, until pH is about 7.It is complete for naked eyes this generates one
The colourless fluids of all-transparent.When being irradiated with arrow beam of light, zinc carbonate colloidal dispersion can be seen in light beam, in above example
That observes is similar.
Example 13
The specification of association is protected to prepare ACQ (ammoniacal copper quaternary) timber preservative sample according to american wood.The sample is to include
The type of copper carbonate, ammonia and Carboquat.It includes the 1.1g basic copper carbonate for being equivalent to 0.83g copper oxide (0.01mol),
Add 0.41g didecyldimethylammonium ammonium carbonate as Carboquat.Addition 0.005mol ammonium hydrogen carbonate (0.4g) adds thereto
The ammonia of 30% aqueous solution form of 2.28g.The sample is a navy blue clear aqueous fluid.
Take the aliquot for being equivalent to 1.1g basic copper carbonate.A kind of (the epoxy second of 0.4g Atlox 4894 is added thereto
Alkane/epoxy propane copolymer non-ionic dispersing agent).As non-ionic dispersing agent, Atlox 4894 and cationic surfactant
Carboquat is compatible.It avoids using anionic surfactant or dispersing agent (such as neopelex), this is because
This can cause to precipitate by reacting with cationic surfactant.
The water being saturated by carbon dioxide is added under vigorous agitation.This generates a copper carbonate powder blue dispersion,
Didecyldimethylammonium ammonium carbonate retains in the solution.
Example 14
It prepares ACQ sample as follows: exposed copper wire being placed in ammonia/ammonium bicarbonate aqueous solution first, is used air as
Oxidant, until copper is completely dissolved.Didecyldimethylammonium ammonium carbonate is added into the aliquot of solution, is obtained such as example 13
Described in ACQ solution.
0.4g Atlox 4894 is added thereto.Then the water being saturated by carbon dioxide is added under vigorous agitation.This is produced
The optically transparent copper carbonate dispersion of a powder blue is given birth to.
Example 15
Basic copper carbonate colloidal dispersion is prepared according to the step of described in above example 7, in addition to Orotan is replaced by
0.3g polyvinylpyrrolidone (K15).This generates a kind of flocculating compositions, and stable sub-micro is provided when being diluted with water
Grain dispersion.
Example 16
Basic copper carbonate colloidal dispersion is prepared according to the step of described in water example 7, in addition to Orotan is replaced by
0.3g polyvinylpyrrolidone (K15).0.1g neopelex in water is added into resulting composition.This generates steady
Fixed subparticle dispersion.The dispersion is stable when further being diluted with water.
Example 17
1.1g (0.005mol) the basic copper carbonate preparation of 0.01mol copper is equivalent to by adding into a reaction vessel
Carbonic acid cuoxam.0.4g (0.005mol) ammonium carbonate is added together with 20ml water.0.3g Orotan 731DP is stirred to this
In solution.Be slowly added ammonia solution (S.G.0.880) under agitation, until basic copper carbonate is completely dissolved, obtain one it is non-
Often dark blue solution.Then 0.6g borax (sodium tetraborate) pentahydrate is added.
The water that addition is saturated at 10 DEG C by carbon dioxide under vigorous agitation, until pH is down to 9.Pass through the vision fluid
Remain transparent blue solution (being transparent blue fluid for naked eye).The fluid is stable mantoquita subparticle colloidal state
Dispersion.
It is believed by the inventors that the fluid may include alkali formula copper borate subparticle.
Example 18
Basic copper carbonate colloidal dispersion is prepared according to the step of described in above example 7, in addition to 0.3g Orotan is substituted
For 0.4g Atlox 4894.
The alkali of stoichiometric amount is carefully added into blue solution, removes carbonate anion for the carbon of generation will pass through
Sour copper is converted into Kocide SD.This is proved by therefrom blue to color change azury.
Then the sample is heated to 80 DEG C, carried out 4 minutes, thus Kocide SD is converted into the copper oxide of black.
Example 19
It is prepared by the step of carbonic acid cuoxam is according to described in example 7.
The water being saturated at 10 DEG C by carbon dioxide is added under agitation, until pH is 8.It is transparent light blue this generates one
The basic copper carbonate subparticle dispersion of color.
Example 20
0.2g sodium tetraborate tetrahydrate is added in the sample of the basic copper carbonate dispersion prepared into above example 19.
After stirring and ensuring to be completely dissolved, pH is measured as 9.Precipitating is not observed;Dispersion keeps transparent.
Example 21
0.2g sodium tetraborate pentahydrate is added in the sample of the dispersion prepared into above example 13.Agitation and it is true
After guarantor is completely dissolved, pH is measured as 9.Precipitating is not observed.
Example 22
Boron is prepared by 1.5g (0.005mol) copper borate that addition is equivalent to 0.005mol copper into a reaction vessel
Sour cuoxam.0.3g Orotan 731DP is stirred in the solution.It is slowly added ammonia solution under agitation
(S.G.0.880), until alkali formula copper borate is completely dissolved, a very dark blue solution is obtained.
The water being saturated at 10 DEG C by carbon dioxide is added under agitation, until pH is 8.It is transparent light blue this generates one
The dispersion of color is considered as alkali formula copper borate subparticle.
Example 23
The specification of association is protected to prepare ACQ (ammoniacal copper quaternary) timber preservative sample according to american wood.The sample is to include
The type of copper carbonate, ammonia and Carboquat.This adds comprising being equivalent to the 1.1g basic copper carbonate of 0.83g copper oxide (0.01mol)
0.41g didecyldimethylammonium ammonium carbonate is as Carboquat.Addition 0.005mol ammonium hydrogen carbonate (0.4g) plus 2.28g thereto
The ammonia of 30% aqueous solution form.The sample is navy blue clear aqueous fluid.
Take the aliquot for being equivalent to 1.1g basic copper carbonate.
The water being saturated by carbon dioxide is added under agitation.This generates the dispersions of the transparent copper carbonate of a powder blue
Body, didecyldimethylammonium ammonium carbonate retain in the solution.
Compared with the step of described in the example 13, it is not added with Altox4894.
Without wishing to be bound by theory, it is believed by the inventors that the subparticle dispersion of insoluble metallic salt is carbonated ammonium
It stabilizes without assembling and/or settling, the ammonium carbonate is formed when adding carbon dioxide in the ammino-complex into solution.
Two molecule ammonium carbonates are generated when adding carbon dioxide and decomposing each soluble metal complex compound.
Example 24
Some plain bar test pieces are added in the sample of the dispersion prepared into example 19 to act on evaluation of corrosion.One week it
The appearance of steel test piece or liquid composition does not change afterwards.
Above example proves that the subparticle dispersion of metal carbonate and/or borate can pass through the simple of low cost
Technology preparation is without using expensive device and equipment to be ground, and corresponding metal hydroxides and metal oxidation
Object can also be prepared by this method.
Industrial applicibility
The composition comprising subparticle generated by means of the present invention can be used for various applications, this is for this field
It will be apparent for technical staff.For example, the composition comprising biocidal metal salt subparticle can be used to handle base
Body is to fight biodegrade or harmful organism.Particularly, the composition can be used to handle lignocellulosic matrix (such as wood
Material), plant (including cereal crops), other biodegradable matrixes (including leather), inorganic matrix (such as concrete), with
And abiotic matrix (such as painting layer).The composition can be used for example for preventing harmful organism organism (such as harmful
Fungi) growth purpose, or for providing specific characteristic for matrix.The subparticle also may include metal compound
Object can be used as pigment, also act as or be converted into catalyst.
Following paragraphs is related to various aspects of the invention and each embodiment:
1. a kind of method for preparing the composition comprising metal salt subparticle, the method includes:
It provides and wraps metalliferous alkaline aqueous solution, one or more can form soluble complexes with metal under alkaline condition
Ligand and one or more dispersing agents;And
Solution is mixed with carbon dioxide source to reduce the pH of solution, so as to metal salt subparticle precipitating, to provide
Water-based composition comprising metal salt subparticle.
2. method described in paragraph 1, wherein the water-based composition is colloidal dispersion;Or the water-based composition is
Flocculated composition, the method is further included goes to flocculate by the composition, to provide colloidal dispersion.
3. method described in paragraph 1 or 2, wherein solution to be mixed to the pH that can reduce solution with carbon dioxide source, so as to gold
Belong to carbonate subparticle precipitating.
4. method described in either segment in aforementioned paragraphs, it includes by solution, carbon dioxide source and one or more weak
The source mixing of acid, to reduce the pH of solution, so as to metal salt subparticle precipitating.
5. method described in paragraph 4, wherein the weak acid is the weak acid of the pKa at least about 6.
6. method described in paragraph 4 or 5, wherein the weak acid is essentially insoluble for that can be formed with metal in the water of pH7
The weak acid of the salt of property.
7. method described in either segment in paragraph 4-6, wherein the weak acid is boric acid or phenol.
8. method described in paragraph 7, wherein the weak acid source is boric acid or borate.
9. method described in either segment in aforementioned paragraphs, wherein the water-based composition includes metal carbonate sub-micro
Grain, and the method is further included the water-based composition alkali process comprising metal carbonate subparticle, to provide
Water-based composition comprising metal hydroxides subparticle;And optionally by the water comprising metal hydroxides subparticle
Property composition heating, with provide include metal oxide subparticle water-based composition.
10. method described in either segment in aforementioned paragraphs, wherein the water-based composition includes metal carbonate sub-micro
Grain or metal hydroxides, the method, which further includes, to be heated comprising the water-based composition of metal carbonate subparticle,
To provide the water-based composition for including metal oxide subparticle.
11. method described in either segment in aforementioned paragraphs, wherein the carbon dioxide source is carbon dioxide gas, includes two
The solution of carbonoxide, potential carbon dioxide source or the wherein arbitrarily combination of two or more.
12. method described in either segment in aforementioned paragraphs, wherein the carbon dioxide source is carbon dioxide gas or packet
Carbonated solution.
13. method described in either segment in aforementioned paragraphs is less than wherein the metal salt has in water at 20 DEG C
The solubility of 0.1g/L.
14. method described in either segment in aforementioned paragraphs, wherein it is about 4.5 to about 9 that the pH of the solution, which is reduced to pH,.
15. method described in either segment in aforementioned paragraphs, wherein offer alkaline aqueous solution includes:
The metalliferous alkaline precursor aqueous solution of packet is provided and one or more can be formed under alkaline condition with metal can
The ligand of molten complex compound;And
Mix one or more dispersing agents.
16. method described in either segment in aforementioned paragraphs, wherein providing alkaline solution or alkaline precursor solution included in packet
Source metal can be formed into soluble complexes with metal under alkaline condition with one or more in aqueous alkalescence medium containing alkali
Ligand reaction.
17. method described in paragraph 16, wherein the alkali is alkali metal hydroxide (such as sodium hydroxide or hydroxide
Potassium), ammonia or amine.
18. method described in paragraph 16 or 17, wherein the source metal is metallic compound or metal element.
19. method described in either segment in aforementioned paragraphs, wherein the pH of the alkaline solution and/or alkaline precursor solution is
At least 9.
20. method described in either segment in aforementioned paragraphs, wherein one or more of ligands are selected from and to be made up of
Group: ammonia, amine and glycol, such as dihydric alcohol, trihydroxylic alcohol and polyalcohol.
21. method described in either segment in aforementioned paragraphs, wherein one or more of ligands are selected from and to be made up of
Group: glycerol, ethylene glycol and ammonia.
22. method described in either segment in aforementioned paragraphs, wherein the metal is first, second or third transition series
Metal.
23. method described in either segment in aforementioned paragraphs, wherein the metal is copper or zinc.
24. method described in either segment in aforementioned paragraphs, wherein alkaline aqueous solution and/or alkaline precursor aqueous solution and/or
Water-based composition includes one or more organic solvents.
25. method described in either segment in aforementioned paragraphs, wherein before alkaline aqueous solution and/or alkalinity comprising subparticle
Body aqueous solution and/or water-based composition further include one or more surfactants.
26. method described in either segment in aforementioned paragraphs, further include by one or more surfactants with comprising
The alkaline solution of subparticle and/or alkaline precursor solution and/or water-based composition mixing.
27. method described in either segment in aforementioned paragraphs, further include by one or more other dispersing agents with
Alkaline solution comprising subparticle and/or water-based composition mixing.
28. method described in either segment in aforementioned paragraphs, wherein the dispersing agent are as follows: anionic dispersing agents, such as poly- carboxylic
Hydrochlorate (such as polyacrylate), naphthalenesulfonate formaldehyde condensation compound, ligninsulfonate, condensate of melamine sulfonate and formaldehyde,
Alkyl-aryl-group ether phosphate or alkyl ether phosphate;Cation dispersing agent;Non-ionic dispersing agent, such as polyethers, including mixing
Polyethers;Amphoteric ion dispersing agent, such as amphoteric ion polymer;Or the wherein arbitrarily combination of two or more.
29. method described in either segment in paragraph 25-28, wherein the surfactant is anionic surfactant,
Such as dodecyl benzene sulfonate, lauryl sulfate or lauryl sulfate;Cationic surfactant, such as benzene are pricked
Oronain or cetyl trimethylammonium bromide;Nonionic surfactant, such as nonylphenol polyoxyethylene ether or octyl phenol polyoxy
Vinethene;Zwitterionic surfactant;Or the wherein arbitrarily combination of two or more.
30. method described in either segment in aforementioned paragraphs is further included through mixed acid or alkali and is adjusted comprising Asia
The pH of the alkaline solution of microparticle and/or alkaline precursor solution and/or water-based composition.
31. method described in either segment in aforementioned paragraphs, wherein the water-based composition comprising subparticle is to mark
To the colloidal dispersion of cohesion and/or settlement stability within 1,2,3,4,5,6 or 7 day period under the conditions of standard.
32. method described in either segment in aforementioned paragraphs, wherein the composition comprising subparticle further includes one kind
Or a variety of biocides.
33. method described in paragraph 32, wherein the biocide be fungicide, it is insecticide, mildewcide, bactericidal
Agent or algicide.
34. method described in either segment in aforementioned paragraphs, further include by one or more biocides with comprising
The composition of subparticle mixes.
35. method described in either segment in paragraph 32-34, wherein one or more biocides be solution, lotion,
Microencapsulation or subparticle form.
36. method described in either segment in aforementioned paragraphs, wherein the composition comprising subparticle includes one or more
The subparticle of biocide.
37. a kind of combination comprising metal salt subparticle by according to the method preparation of either segment in aforementioned paragraphs
Object.
38. a kind of method for handling matrix, the method includes to apply to matrix by according to any one of aforementioned paragraphs
Method preparation the composition comprising metal salt subparticle.
39. a kind of matrix by being handled according to the method for paragraph 38.
Although the present invention is described by way of example and with reference to specific embodiment, it should be appreciated that can
It modifies and/or changes in the case of without departing from the scope of the present invention.
The complete disclosure of all applications, patent and publication (if any) that above and below is quoted all passes through
It is incorporated herein by reference.
Claims (54)
1. a kind of method for preparing the composition comprising metal salt subparticle, the method includes:
It provides and wraps metalliferous alkaline aqueous solution, one or more can form soluble complexes with the metal under alkaline condition
Ligand and optional one or more dispersing agents;And
The solution and carbon dioxide source are mixed, to reduce the pH of the solution, so as to metal salt subparticle precipitating, thus
The water-based composition of subparticle comprising the metal salt is provided.
2. according to the method described in claim 1, wherein the method includes:
It provides and wraps metalliferous alkaline aqueous solution, one or more can form soluble complexes with the metal under alkaline condition
Ligand and one or more dispersing agents.
3. method according to claim 1 or 2, wherein the water-based composition is colloidal dispersion;Or it is described aqueous
Composition is flocculating composition, and the method is further included goes to flocculate by the composition, to provide colloidal dispersion.
4. according to the method in any one of claims 1 to 3, wherein the solution is mixed meeting with the carbon dioxide source
The pH of the solution is reduced, so as to metal carbonate subparticle precipitating.
5. method according to claim 1 to 4, wherein the solution is mixed meeting with the carbon dioxide source
The pH of the solution is reduced, so as to metal borate subparticle precipitating.
6. method according to any of the preceding claims, wherein the soluble metal complex compound is reducing the alkali
It can be decomposed when the pH of property solution.
7. method according to any of the preceding claims, wherein the soluble metal complex compound can be with the dioxy
Change the carbon dioxide reaction that carbon source provides.
8. method according to any of the preceding claims, wherein the one or more of the soluble metal complex compound
Ligand is discharged from the soluble metal complex compound and/or one or more ligands of the soluble metal complex compound
Salt generated by the decomposition of the soluble metal complex compound.
9. method according to any of the preceding claims, wherein one or more of ligands or its salt can reduce or
Prevent the aggregation and/or sedimentation of the subparticle.
10. method according to any of the preceding claims, wherein one or more of ligands or its salt are selected from carbon
The carbonate and glycol of sour ammonium, amine.
11. method according to any of the preceding claims, wherein the solution further include it is one or more weak
The source of acid.
12. method according to any of the preceding claims, it includes by the solution, carbon dioxide source, Yi Jiyi
The source of kind or a variety of weak acid mixing, to reduce the pH of the solution, so as to metal salt subparticle precipitating.
13. according to the method for claim 12, wherein the weak acid is the weak acid of the pKa at least about 6.
14. method according to claim 12 or 13, wherein the weak acid is that can be formed with the metal in the water of pH7
The weak acid of the salt of essentially insoluble property.
15. method described in any one of 2-14 according to claim 1, wherein the weak acid is boric acid or phenol.
16. according to the method for claim 15, wherein the source of the weak acid is boric acid or borate.
17. method according to any of the preceding claims, wherein the water-based composition includes the carbon of the metal
The subparticle of hydrochlorate, and the method is further included the described aqueous of the carbonate subparticle comprising the metal
Composition alkali process, to provide the water-based composition of the hydroxide subparticle comprising the metal;And optionally will
The water-based composition of hydroxide subparticle comprising the metal heats, to provide the oxide for including the metal
The water-based composition of subparticle.
18. method according to any of the preceding claims, wherein the water-based composition includes the carbon of the metal
The subparticle of the hydroxide of hydrochlorate or the metal, and the method is further included the carbonic acid comprising the metal
The water-based composition of the subparticle of salt heats, to provide aqueous group of the subparticle of the oxide comprising the metal
Close object.
19. method according to any of the preceding claims, wherein the carbon dioxide source is carbon dioxide gas, packet
Carbonated solution, potential carbon dioxide source or the wherein arbitrarily combination of two or more.
20. method according to any of the preceding claims, wherein the carbon dioxide source be carbon dioxide gas or
Person wraps carbonated solution.
21. method according to any of the preceding claims, wherein the metal salt is at 20 DEG C in water with small
In the solubility of 0.1g/L.
22. method according to any of the preceding claims, wherein it is about 4.5 to about that the pH of the solution, which is reduced to pH,
9。
23. method according to any of the preceding claims, wherein the pH of the solution be reduced to pH be about 7.5 to
9.5。
24. method according to any of the preceding claims, wherein it is about 8 to 9 that the pH of the solution, which is reduced to pH,.
25. method according to any of the preceding claims, wherein providing the alkaline aqueous solution and including:
There is provided the metalliferous alkaline precursor aqueous solution of packet and it is one or more can be formed under alkaline condition with the metal it is solvable
The ligand of complex compound;And
Optionally mix one or more dispersing agents.
26. method according to any of the preceding claims, wherein providing the alkaline aqueous solution and including:
There is provided the metalliferous alkaline precursor aqueous solution of packet and it is one or more can be formed under alkaline condition with the metal it is solvable
The ligand of complex compound;And
Mix the one or more dispersing agents.
27. method according to any of the preceding claims, wherein providing the alkaline solution or alkaline precursor solution
Include in the aqueous alkalescence medium comprising alkali by the source of the metal with it is one or more under alkaline condition can with it is described
The ligand reaction of metal formation soluble complexes.
28. according to the method for claim 27, wherein the alkali is alkali metal hydroxide (such as sodium hydroxide or hydrogen-oxygen
Change potassium), ammonia or amine.
29. the method according to claim 27 or 28, wherein the source of the metal is metallic compound or metal element.
30. method according to any of the preceding claims, wherein the alkaline solution and/or alkaline precursor solution
PH is at least 9.
31. method according to any of the preceding claims, wherein one or more of ligands are selected from by with the following group
At group: ammonia, amine and glycol, such as dihydric alcohol, trihydroxylic alcohol and polyalcohol.
32. method according to any of the preceding claims, wherein one or more of ligands are selected from by with the following group
At group: glycerol, ethylene glycol and ammonia.
33. method according to any of the preceding claims, wherein the metal is first, second or third transition
Series metal.
34. method according to any of the preceding claims, wherein the metal is copper or zinc.
35. method according to any of the preceding claims, wherein the alkaline aqueous solution and/or alkaline precursor are water-soluble
Liquid and/or water-based composition include one or more organic solvents.
36. method according to any of the preceding claims, wherein the alkaline aqueous solution comprising subparticle and/
Or alkaline precursor aqueous solution and/or water-based composition further include one or more surfactants.
37. method according to any of the preceding claims is further included one or more surfactants
It is mixed with the alkaline solution comprising subparticle and/or alkaline precursor solution and/or the water-based composition.
38. method according to any of the preceding claims is further included one or more other dispersions
Agent is mixed with the alkaline solution comprising subparticle and/or the water-based composition.
39. method according to any of the preceding claims, wherein the dispersing agent are as follows: anionic dispersing agents, such as
The polycarboxylate of such as polyacrylate, naphthalenesulfonate formaldehyde condensation compound, ligninsulfonate, melamine sulfonate and formaldehyde condensation
Object, alkyl-aryl-group ether phosphate or alkyl ether phosphate;Cation dispersing agent;Non-ionic dispersing agent, it is poly- for example including mixing
The polyethers or polyvinylpyrrolidone of ether;Amphoteric ion dispersing agent, such as amphoteric ion polymer;Or wherein any two kinds
Or more combination.
40. the method according to any one of claim 36-39, wherein the surfactant are as follows: anionic surface is living
Property agent, such as dodecyl benzene sulfonate, lauryl sulfate or lauryl sulfate;Cationic surfactant, such as
Benzalkonium chloride or cetyl trimethylammonium bromide;Nonionic surfactant, such as nonylphenol polyoxyethylene ether or octyl phenol
Polyoxyethylene ether;Zwitterionic surfactant;Or the wherein arbitrarily combination of two or more.
41. method according to any of the preceding claims, further includes and include by mixed acid or alkali adjusting
The pH of the alkaline solution of subparticle and/or the alkaline precursor solution and/or the water-based composition.
42. according to the method for claim 41, wherein pH is adjusted by mixing boric acid and/or the borate as borax
Section.
43. method according to any of the preceding claims, wherein the water-based composition comprising subparticle
It is about 7.5 to 9.5 that pH, which is adjusted to pH by mixed acid or alkali,.
44. method according to any of the preceding claims, wherein the water-based composition comprising subparticle
It is about 8 to 9 that pH, which is adjusted to pH by mixed acid or alkali,.
45. method according to any of the preceding claims, wherein the water-based composition comprising subparticle is
At the standard conditions to the colloidal dispersion of cohesion and/or settlement stability within 1,2,3,4,5,6 or 7 day period.
46. method according to any of the preceding claims, wherein the composition comprising subparticle is further
Include one or more biocides.
47. according to the method for claim 46, wherein the biocide is fungicide, insecticide, mildewcide, kills
Bacteriocin or algicide.
48. method according to any of the preceding claims, further include by one or more biocides with
Composition mixing comprising subparticle.
49. the method according to any one of claim 46-48, wherein one or more biocides be solution,
Lotion, microencapsulation or subparticle form.
50. method according to any of the preceding claims, wherein the composition comprising subparticle is further
Subparticle comprising one or more biocides.
51. method according to any of the preceding claims, wherein when using the 12 Corrosion standards method of AWPAE
When test, the composition can generate at least low 20% mpy compared with standard ACQ.
52. a kind of group comprising metal salt subparticle prepared by method according to any of the preceding claims
Close object.
53. a kind of method for handling matrix, the method includes to apply to described matrix by appointing according in preceding claims
The composition comprising metal salt subparticle of the preparation of method described in one.
54. a kind of matrix by being handled according to the method for claim 53.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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NZ721031 | 2016-06-10 | ||
NZ72103116 | 2016-06-10 | ||
PCT/IB2017/053141 WO2017212368A1 (en) | 2016-06-10 | 2017-05-29 | Submicron particle compositions |
Publications (1)
Publication Number | Publication Date |
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CN109641366A true CN109641366A (en) | 2019-04-16 |
Family
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Family Applications (1)
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CN201780038033.7A Pending CN109641366A (en) | 2016-06-10 | 2017-05-29 | Subparticle composition |
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US (1) | US20190255730A1 (en) |
EP (1) | EP3468755A4 (en) |
JP (1) | JP2019520302A (en) |
KR (1) | KR20190038534A (en) |
CN (1) | CN109641366A (en) |
AU (1) | AU2017278043A1 (en) |
CA (1) | CA3025903A1 (en) |
CL (1) | CL2018003542A1 (en) |
WO (1) | WO2017212368A1 (en) |
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FR3092727B1 (en) * | 2019-02-19 | 2023-05-12 | Upl Ltd | Process for the preparation of copper compounds |
CN115336592B (en) * | 2022-07-20 | 2023-10-13 | 福州市福塑科学技术研究所有限公司 | Preparation method of nano copper oxide antibacterial material |
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CN1835830A (en) * | 2003-06-17 | 2006-09-20 | 法布罗技术有限公司 | Particulate wood preservative and method for producing same |
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US6896908B2 (en) * | 2001-01-30 | 2005-05-24 | U.S. Borax Inc. | Wood preservative concentrate |
US20050037221A1 (en) * | 2002-07-31 | 2005-02-17 | Fox Roger F. | Penetration improvement of copper amine solutions into dried wood by addition of carbon dioxide |
JP3703479B2 (en) * | 2002-09-20 | 2005-10-05 | 松下電器産業株式会社 | Nanoparticle production method and nanoparticle produced by the production method |
US20080131666A1 (en) * | 2003-07-31 | 2008-06-05 | Fox Roger F | Penetration improvement of copper amine solutions into dried wood by addition of carbon dioxide |
US20070207076A1 (en) * | 2006-03-06 | 2007-09-06 | Osmose Inc. | Method of preparing metal-containing wood preserving compositions |
US7411080B2 (en) * | 2006-05-19 | 2008-08-12 | Phibro-Tech, Inc. | Direct synthesis of copper carbonate |
KR20090035800A (en) * | 2007-10-08 | 2009-04-13 | 주식회사 에이스켐텍 | Timber preservative |
BRPI0819397A2 (en) * | 2007-12-13 | 2014-10-07 | Union Carbide Chem Plastic | AQUOSOUS PRESERVATIVE COMPOSITION TO TREAT BIODEGRADABLE SUBSTRATES |
JP5576303B2 (en) * | 2008-03-14 | 2014-08-20 | ユニオン カーバイド ケミカルズ アンド プラスティックス テクノロジー エルエルシー | A hybrid method for reducing leaching of metal biocides from biodegradable substrates |
US20090324481A1 (en) * | 2008-06-27 | 2009-12-31 | Jeff Miller | Low energy method of preparing basic copper carbonates |
CN104512952A (en) * | 2013-09-27 | 2015-04-15 | 中国石油天然气股份有限公司 | Method for recycling zinc from zinc ammonia solution |
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2017
- 2017-05-29 JP JP2019517185A patent/JP2019520302A/en active Pending
- 2017-05-29 AU AU2017278043A patent/AU2017278043A1/en not_active Abandoned
- 2017-05-29 KR KR1020197000192A patent/KR20190038534A/en unknown
- 2017-05-29 CN CN201780038033.7A patent/CN109641366A/en active Pending
- 2017-05-29 US US16/308,336 patent/US20190255730A1/en not_active Abandoned
- 2017-05-29 EP EP17809807.5A patent/EP3468755A4/en not_active Withdrawn
- 2017-05-29 CA CA3025903A patent/CA3025903A1/en not_active Abandoned
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EP3468755A1 (en) | 2019-04-17 |
KR20190038534A (en) | 2019-04-08 |
US20190255730A1 (en) | 2019-08-22 |
CA3025903A1 (en) | 2017-12-14 |
CL2018003542A1 (en) | 2019-07-12 |
AU2017278043A1 (en) | 2018-12-13 |
WO2017212368A1 (en) | 2017-12-14 |
JP2019520302A (en) | 2019-07-18 |
EP3468755A4 (en) | 2019-12-04 |
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